CN102224157A - Novel compound, process for producing the compound, organic semiconductor material, and organic semiconductor device - Google Patents

Novel compound, process for producing the compound, organic semiconductor material, and organic semiconductor device Download PDF

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CN102224157A
CN102224157A CN2009801464744A CN200980146474A CN102224157A CN 102224157 A CN102224157 A CN 102224157A CN 2009801464744 A CN2009801464744 A CN 2009801464744A CN 200980146474 A CN200980146474 A CN 200980146474A CN 102224157 A CN102224157 A CN 102224157A
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naphthalene
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CN102224157B (en
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泷宫和男
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NAT UNIVERSITY OF CORP HIROSHI
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D517/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having selenium, tellurium, or halogen atoms as ring hetero atoms
    • C07D517/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having selenium, tellurium, or halogen atoms as ring hetero atoms in which the condensed system contains two hetero rings
    • C07D517/04—Ortho-condensed systems
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having a potential-jump barrier or a surface barrier
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H—ELECTRICITY
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having a potential-jump barrier or a surface barrier
    • H10K10/40—Organic transistors
    • H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
    • H10K10/462—Insulated gate field-effect transistors [IGFETs]
    • H10K10/464—Lateral top-gate IGFETs comprising only a single gate
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having a potential-jump barrier or a surface barrier
    • H10K10/40—Organic transistors
    • H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
    • H10K10/462—Insulated gate field-effect transistors [IGFETs]
    • H10K10/466—Lateral bottom-gate IGFETs comprising only a single gate

Abstract

Disclosed are a novel compound having good electron mobility, a process for producing the compound, an organic semiconductor material containing the compound, and an organic semiconductor device. The respective novel compounds have a structure comprising naphthalene and a thiophene ring or a selenophene ring bonded to each of two benzene rings in the naphthalene, as represented by general formula (1), (2), (3), or (4) wherein Z represents a sulfur atom or a selenium atom; and R represents a hydrogen atom, an alkyl group, or a phenyl group. Each of the compounds has a conjugated system within each molecule derived from an interaction between p orbits, and exhibits a strong molecule interaction through a sulfur atom or a selenium atom contained in the thiophene ring or the selenophene ring in each molecule. Thus, the compound has a good electron mobility.

Description

Novel cpd and preparation method thereof, organic semiconductor material and organic semiconductor device
Technical field
The present invention relates to novel cpd and preparation method thereof, organic semiconductor material and organic semiconductor device.
Background technology
In recent years, membrane unit such as organic EL (electroluminescent) device of use organic semiconductor material, organic FET (field-effect transistor) device, organic film photoelectric conversion device are noticeable, beginning practicability.
In the basic physical properties of the organic semiconductor material that uses in these membrane unit, the mobility of electric charge carrier (being designated hereinafter simply as " current carrier ") is important.For example in the organic El device, carrier mobility influences the transmission efficiency of electric charge.In order to improve luminous efficiency, to drive under low voltage, the transmission efficiency of electric charge is important.In addition, in the organic FET device, the mobility of charge carrier rate directly influences the performance of transistorized switching speed, driven device.Therefore, carrier mobility also is important for the practicability and the performance raising of organic FET device.
Under this situation, carrying out can be used as the research and development of the various organic compound that organic semiconductor material uses.As compound, has the compound of benzene-thiophene skeleton in research with suitable carrier mobility.In the non-patent literature 1, illustration various compounds with benzene-thiophene skeleton.
The prior art document
Non-patent literature
Non-patent literature 1:Vibronic Coupling in Organic Semiconductors:The Case of Fused Polycyclic Benzene-Thiophene Structures; Veaceslav Coropceanu, Ohyun Kwon, Brigitte Wex, Bilal R.Kaafarani, Nadine E.Gruhn, Jason C.Durivage, Douglas C.Neckers and Jean-Luc Bredas; Chem.Eur.J.2006, Vol.12, p.2073-2080
Summary of the invention
In non-patent literature 1, exemplified and had naphthalene-structural formula of the compound of thiophene skeleton.But such compound is also not successful as yet at present synthetic compound, that is to say the compound that reality does not exist as yet.According to the knowledge of known Synthetic Organic Chemistry, it is extremely difficult importing thiphene ring in the naphthalene skeleton.
The object of the present invention is to provide to have naphthalene-the good novel cpd of thiophene skeleton or naphthalene-selenium phenol (Selenophene) skeleton, carrier mobility and preparation method thereof, and organic semiconductor material and the organic semiconductor device that contains this compound is provided.
The compound of the 1st aspect is by following formula (1), formula (2), formula (3) or the represented compound of formula (4) according to the present invention.
Figure BPA00001373358600021
(in the above-mentioned formula, Z represents sulphur atom or selenium atom, and R represents hydrogen atom, alkyl or phenyl.)
The compound of the 2nd aspect is by following formula (5), formula (6), formula (7) or the represented compound of formula (8) according to the present invention.
Figure BPA00001373358600022
(in the above-mentioned formula, Z represents sulphur atom or selenium atom, and X represents halogen atom.)
Preparation method according to the compound of the 3rd aspect of the present invention is the preparation method of the represented compound of following formula (1), formula (2), formula (3) or formula (4), may further comprise the steps: make the reaction of dihalo-dihydroxy naphthlene and Trifluoromethanesulfonic anhydride and obtain the step of dihalo--two (trifluoromethane sulphonyl) naphthalene; Make the reaction of above-mentioned dihalo--two (trifluoromethane sulphonyl) naphthalenes and terminal alkynyl compounds and obtain the step of dihalo--diacetylene naphthalene derivatives; And the step that makes above-mentioned dihalo--diacetylene naphthalene derivatives and sulphide salt or selenide reactant salt.
Figure BPA00001373358600031
(in the above-mentioned formula, Z represents sulphur atom or selenium atom, and R represents hydrogen atom, alkyl or phenyl.)
The preparation method of the compound of the 3rd aspect of the present invention can also may further comprise the steps: make the reaction of dihydroxy naphthlene and halogenating agent obtain the step of above-mentioned dihalo-dihydroxy naphthlene.
Alternatively, above-mentioned dihydroxy naphthlene is 2, and 6-dihydroxy naphthlene, the compound of gained are by above-mentioned formula (1) or the represented compound of above-mentioned formula (3).
In addition, alternatively, above-mentioned dihydroxy naphthlene is a 2,7 dihydroxy naphthalene, and the compound of gained is by the represented compound of above-mentioned formula (2).
In addition, alternatively, above-mentioned dihydroxy naphthlene is 1, and 5-dihydroxy naphthlene, the compound of gained are by the represented compound of above-mentioned formula (4).
Preferably, above-mentioned halogenating agent is bromizating agent or chlorizating agent.
Preferably, above-mentioned halogenating agent is a bromizating agent, and the preparation method of this compound also comprises and add to promote above-mentioned dihydroxy naphthlene to carry out the step of the catalyzer of bromination, and the step of adding above-mentioned bromizating agent is carried out more than 2 times.
In addition, preferably, the above-mentioned end alkynyl compounds is trimethylsilyl acetylene, phenylacetylene, any in the 1-decine.
In addition, preferably, being reflected in the polar solvent that can dissolve above-mentioned dihalo--two (trifluoromethane sulphonyl) naphthalene of above-mentioned dihalo--two (trifluoromethane sulphonyl) naphthalene and above-mentioned end alkynyl compounds carried out.
In addition, preferably, above-mentioned polar solvent is non-protic polar solvent.
In addition, preferably, above-mentioned non-proton property polar solvent is a dimethyl formamide.
Preparation method according to the compound of the 4th aspect of the present invention is the preparation method of the represented compound of following formula (5), formula (6), formula (7) or formula (8),
Figure BPA00001373358600041
(in the above-mentioned formula, Z represents sulphur atom or selenium atom, and R represents hydrogen atom.)
This method is included in the step of adding halogenating agent in the represented compound of following formula (1), formula (2), formula (3) or formula (4).
Figure BPA00001373358600042
(in the above-mentioned formula, Z represents sulphur atom or selenium atom, and X represents halogen atom.)
According to the feature of the organic semiconductor material of the 5th aspect of the present invention is that to contain the represented compound of more than one following formulas (1), formula (2), formula (3) or formula (4) a kind of.
(in the above-mentioned formula, Z represents sulphur atom or selenium atom, and R represents hydrogen atom, alkyl or phenyl.)
Be characterised in that the organic semiconductor material that contains the of the present invention the 5th aspect according to the organic semiconductor device of the 6th aspect of the present invention.)
The invention effect
According to compound of the present invention, has naphthalene-thiophene skeleton or naphthalene-selenium phenol skeleton.This compound is because the interaction of π track and have conjugated system at each intramolecularly, and demonstrates the intermolecular stronger interaction that produces by the sulphur atom that contains in the thiphene ring of each molecule or selenium phenol ring or selenium atom.Therefore, can carry out mobility of charge carrier effectively.According to compound of the present invention,, can be used as organic semiconductor material and use owing to have good electric field mobility.This organic semiconductor material can be used for organic semiconductor device.
In addition, according to the preparation method of compound of the present invention, can prepare by dihalo--diacetylene naphthalene derivatives and have naphthalene-compound of thiophene skeleton or naphthalene-selenium phenol skeleton.
In addition, according to the preparation method of compound of the present invention, can be optionally the hydrogen atom of naphthalene be carried out halogenation.According to this preparation method, can improve and have naphthalene-yield of the compound of thiophene skeleton or naphthalene-selenium phenol skeleton.
Description of drawings
Fig. 1 is the figure that shows the schematic configuration of the FET element for preparing among the embodiment, (A) is the sectional view of FET element, (B) is its orthographic plan.
(A) of Fig. 2 is to use the Vg-Id curve of the FET element of compd A preparation, (B) is its Vd-Id curve.
(A) of Fig. 3 is to use the Vg-Id curve of the FET element of compd B preparation, (B) is its Vd-Id curve.
(A) of Fig. 4 is to use the Vg-Id curve of the FET element of Compound C preparation, (B) is its Vd-Id curve.
(A) of Fig. 5 is to use the Vg-Id curve of the FET element of Compound D preparation, (B) is its Vd-Id curve.
Embodiment
Below, describe the embodiment of novel cpd of the present invention and preparation method thereof and organic semiconductor material and organic semiconductor device in detail.
Novel cpd
Novel cpd according to the 1st embodiment of the present invention is to be combined with the compound of thiphene ring or selenium phenol ring on formula described as follows (1), formula (2), formula (3) or formula (4) 2 phenyl ring represented, that contain in naphthalene respectively.
Figure BPA00001373358600061
(in the above-mentioned formula, Z represents sulphur atom or selenium atom, and R represents hydrogen atom, alkyl or phenyl.)
2 R that contain in each compound both can be identical substituting groups, also can be mutual different substituting groups, but preferably identical substituting group.
As alkyl, comprise for example methyl, ethyl, n-propyl, normal-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, the n-undecane base, dodecyl, the n-tridecane base, n-tetradecane base group, the Pentadecane base, the n-hexadecyl group, the n-heptadecane base, positive alkyl saturated straight chain group such as octadecyl, sec.-propyl, isobutyl-, sec-butyl, the saturated butyl of tertiary alkyl and side chain, cyclopropyl, saturated cyclic alkyls such as cyclobutyl, the 1-propenyl, the 2-propenyl, the 1-butylene base, crotyl, unsaturated alkyls such as 3-butenyl.
By above-mentioned formula (1) to the represented compound of formula (4), because the interaction of π track has conjugated system at each intramolecularly, and demonstrate the intermolecular stronger interaction that produces by the sulphur atom that in the thiphene ring of each molecule or selenium phenol ring, contains or selenium atom.Therefore, above-mentioned formula (1) can be carried out mobility of charge carrier effectively to the represented compound of formula (4), has good electric field mobility.These compounds can be used as organic semiconductor material and use.
The novel cpd of the 2nd embodiment of the present invention is represented by following formula (5), formula (6), formula (7) or formula (8).
Figure BPA00001373358600062
(in the above-mentioned formula, Z represents sulphur atom or selenium atom, and X represents halogen atom.)
As halogen atom, comprise for example chlorine, bromine, iodine etc.
The preparation method of novel cpd
Then, preparation method by above-mentioned formula (1), formula (2), formula (3) and the represented compound of formula (4) sequentially is described.
At first, make the reaction of dihydroxy naphthlene and halogenating agent, synthetic dihalo-dihydroxy naphthlene.
As dihydroxy naphthlene, use on 2 the phenyl ring in naphthalene, containing respectively material in conjunction with 1 hydroxyl.In such dihydroxy naphthlene, preferred 2,6-dihydroxy naphthlene, 2,7 dihydroxy naphthalene or 1,5-dihydroxy naphthlene.
As halogenating agent, can use known material.For example can suitably use bromizating agents such as bromine, N-bromo-succinimide, pyridinium bromide perbromide or tetraalkyl tribromide ammonia, or chlorizating agents such as chlorine, N-chlorosuccinimide, tetraalkyl tri-chlorination ammonium, thionyl chloride or sulfuryl chloride.
Then, with resulting dihalo-dihydroxy naphthlene and Trifluoromethanesulfonic anhydride (CF 3SO 2-O-SO 2CF 3) react.2 hydroxyls that contain in the dihalo-dihydroxy naphthlene and Trifluoromethanesulfonic anhydride reaction convert the trifluoromethayl sulfonic acid ester to.Its result obtains dihalo--two (trifluoromethane sulphonyl) naphthalene.
Then, dihalo--two (trifluoromethane sulphonyl) naphthalenes and the terminal alkynyl compounds with gained reacts.Trifluoromethane sulfonyl group institute bonded carbon is substituted, thereby obtains dihalo--diacetylene naphthalene derivatives.
As terminal alkynyl compounds, for example can use trimethylsilyl acetylene (HC 2Si (CH 3) 3), phenylacetylene (C 8H 6), 1-decine (C 10H 18) etc.
The reaction of dihalo--two (trifluoromethane sulphonyl) naphthalene and terminal alkynyl compounds is preferably carried out in the polar solvent that can dissolve dihalo--two (trifluoromethane sulphonyl) naphthalene.By in polar solvent, reacting, trifluoromethane sulfonyl group is optionally replaced by ethynyl.Thus, can improve the yield of resulting dihalo--diacetylene naphthalene derivatives.Can reduce the waste of employed reagent by improving the dihalo--yield of diacetylene naphthalene derivatives, reduce preparation cost.
As polar solvent, preferably use non-proton property polar solvent.As non-proton property polar solvent, comprise for example dimethyl formamide (DMF), tetrahydrofuran (THF) (THF) etc.Need to prove that the polarity of employed non-proton property polar solvent is high more, the yield of the dihalo-of gained-diacetylene naphthalene derivatives is high more.Therefore, wherein especially preferably use the highest dimethyl formamide of polarity.
Then, the dihalo--diacetylene naphthalene derivatives of gained and sulphide salt or selenide salt are reacted.In this step, the halogen atom that contains in dihalo--diacetylene naphthalene derivatives is replaced by sulphur atom or selenium atom.Sulphur atom that imports or selenium atom and the triple bond phase reaction of the ethynyl of importing in advance form thiphene ring or selenium phenol ring.Like this, can obtain by above-mentioned formula (1) to the represented compound of formula (4).
As sulphide salt, preferably use the sulfide metal-salt, more preferably use the sulfide an alkali metal salt.For example, preferred nine water cure sodium (Na 2S9H 2O), five water cure sodium (Na 2S5H 2O), Sodium sulphate anhydrous, 99min (Na 2S), Sodium sulfhydrate water and thing (NaSHnH 2O) etc.As selenide salt, can use can the commercial selenide salt that obtains.Perhaps, also can for example obtain selenide salt, it is not separated and use by known method such as metallic selenium and sodium borohydride reaction are derived.
Employed sulphide salt in reaction with respect to 1 mole of dihalo--diacetylene naphthalene derivatives, is used 1～16 mole usually.2～8 moles of preferred uses are more preferably used 2～5 moles.
Can use reaction solvent, also can not use reaction solvent, but during as solid, preferably use solvent at the dihalo-that uses-diacetylene naphthalene derivatives.At this moment, preferably containing boiling point in the reaction mixture is solvent more than 100 ℃.Because by contain boiling point in reaction mixture is solvent more than 100 ℃, that temperature of reaction can be set is higher, therefore can improve speed of response.
As the solvent of boiling point more than 100 ℃, comprise for example N-N-methyl-2-2-pyrrolidone N-(NMP), N, amidess such as dinethylformamide, N,N-dimethylacetamide, glycolss such as ethylene glycol, propylene glycol, polyoxyethylene glycol, sulfoxide classes such as dimethyl sulfoxide (DMSO).
Above-mentioned with respect to 1 mole of dihalo--diacetylene naphthalene derivatives, above-mentioned solvent uses 0.01～100 mole usually.0.1～80 mole of preferred use, more preferably 20～50 moles.
Can under-50 ℃～300 ℃ temperature of reaction, react.Preferably, more preferably under 40 ℃～200 ℃, react at-10 ℃～250 ℃.
Among the present invention,, under the situation that reaction can be carried out swimmingly, can add catalyzer in each stage though be not to add catalyzer.Catalyzer as promoting cyclization can exemplify metallic copper or cupric chloride (I), cupric chloride (II), cupric bromide (I), cupric bromide (II), cupric iodide (I) or cupric iodide metal halides such as (II).Preferable alloy copper or cupric bromide (I) or cupric bromide copper halides such as (II).
In addition, as required, by known method, separating, make with extra care from reaction mixture is target compound.In order to obtain highly purified target compound, for example can carry out sublimation purifying, particularly vacuum-sublimation and make with extra care.
Preparation method by the represented compound of above-mentioned formula (1) is specifically described.When synthetic compound by the represented trans linear structure of above-mentioned formula (1), can use 2 as dihydroxy naphthlene, the 6-dihydroxy naphthlene.At this moment, as halogenating agent, can use bromizating agent.
In order to obtain the compound by the represented such linear structure of formula (1), needing will be 2, and the bonded hydrogen atom is replaced to halogen atom on 3 of the 6-dihydroxy naphthlene and 7 s' the carbon atom.Using under the situation of chlorizating agent as halogenating agent, because bonded hydrogen atom on reactive high 1 and 5 s' the carbon atom in the hydrogen atom that the chlorine atom can replace in the dihydroxy naphthlene to be contained, and be difficult to be substituted in bonded hydrogen atom on 3 and 7 s' the carbon atom.
Relative therewith, be used as halogenating agent by the bromizating agent that uses bromine etc., the bonded hydrogen atom also can be replaced by bromine atoms with comparalive ease on 3 and 7 s' the carbon atom.Concrete, for example make by bromizating agent at first that the bonded hydrogen atom is replaced by bromine atoms on reactivity high 1 and 5 s' carbon atom.Then, add to promote the catalyzer of bromination, for example iron etc.In the presence of catalyzer, add bromizating agent several times successively, make that the bonded hydrogen atom also is substituted on 3 and 7 s' carbon atom, can obtain 1,3,5,7-tetrabromobisphenol, 6-dihydroxy naphthlene.
By aforesaid method, can obtain 1,3,5 with high yield (more than 50%), 7-tetrabromobisphenol, 6-dihydroxy naphthlene.With " Reaction of Tetrasulfur Tetranitride with Naphthalenols and Related Compounds " (Bull.Chem.Soc.Jpn., Vol.64, p.68-73; Shuntaro Mataka, Kazufumi Takahashi, Youji Ikezaki, Taizo Hatta, Akiyoshi Torii, Masashi Tashiro) put down in writing in 1,3,5, the 7-tetrabromobisphenol, the synthetic yield 4% of 6-dihydroxy naphthlene is compared as can be known, and this is very high value.
Then, use spongy tin (laminar tin) etc. with this 1,3,5,7-tetrabromobisphenol, the reduction of 6- dihydroxy naphthlene.Make 1 and 5 go up the bonded bromine atoms and replaced, obtain 3,7-two bromo-2,6 dihydroxy naphthlenes by hydrogen atom.
Use this 3,7-two bromo-2,6 dihydroxy naphthlenes, implement with the reaction of above-mentioned Trifluoromethanesulfonic anhydride, with the reaction of terminal alkynyl compounds and with the reaction of sulphide salt or selenide salt.Through these each steps, can optionally obtain the compound of the represented trans linear structure of formula (1).According to this method, can obtain 1,3,5 with above-mentioned high like this yield, 7-tetrabromobisphenol, 6-dihydroxy naphthlene.Therefore, can effectively utilize reagent, reduce preparation cost.
Then, the preparation method by the represented compound of above-mentioned formula (2) is specifically described.When synthesizing the compound of the cis linear structure of representing by above-mentioned formula (2),, can use 2,7 dihydroxy naphthalene as dihydroxy naphthlene.As halogenating agent, can use bromizating agent.If the bromizating agent of 2,7 dihydroxy naphthalene and bromine etc. is reacted, because 8 sterically hindered, when tribromide, react and just stopped, obtaining 1,3,6-three bromo-2,7 dihydroxy naphthalenes.By it being used spongy tin etc. reduce, can obtain 3,6-two bromo-2,7 dihydroxy naphthalenes.Use this 3,6-two bromo-2,7 dihydroxy naphthalenes, implement with the reaction of above-mentioned Trifluoromethanesulfonic anhydride, with the reaction of terminal alkynyl compounds and with the reaction of sulphide salt or selenide salt.Through these each steps, can optionally obtain compound by the represented cis linear structure of formula (2).
Then, the preparation method by the represented compound of above-mentioned formula (3) is specifically described.During by the represented compound of formula (3), as dihydroxy naphthlene, can use 2, the 6-dihydroxy naphthlene synthetic.As halogenating agent, can use chlorizating agents such as chlorine.By 2, the reaction of 6-dihydroxy naphthlene and chlorizating agent can obtain 1 once going on foot, 5-two chloro-2,6-dihydroxy naphthlene.Use this 1,5-two chloro-2, the 6-dihydroxy naphthlene, implement with the reaction of above-mentioned Trifluoromethanesulfonic anhydride, with the reaction of terminal alkynyl compounds and with the reaction of sulphide salt or selenide salt.Through these each steps, can optionally obtain by the represented compound of formula (3).
Then, the preparation method by the represented compound of above-mentioned formula (4) is specifically described.During by the represented compound of formula (4), as dihydroxy naphthlene, can use 1 synthetic, the 5-dihydroxy naphthlene comes.As halogenating agent, can use bromizating agents such as bromine.By 1, the reaction of 5-dihydroxy naphthlene and bromizating agent can obtain 2 once going on foot, 6-two bromo-1,5-dihydroxy naphthlene.Use this 2,6-two bromo-1, the 5-dihydroxy naphthlene, implement with the reaction of above-mentioned Trifluoromethanesulfonic anhydride, with the reaction of terminal alkynyl compounds and with the reaction of sulphide salt or selenide salt.Pass through these each steps, can optionally obtain by the represented compound of formula (4).
Then, to describing by the preparation method of above-mentioned formula (5) to the represented compound of formula (8).
Of the present invention by above-mentioned formula (5) to the preparation method of the represented compound of formula (8), for example by aforesaid method obtain by formula (1) to formula (4) represented and R be in the compound of hydrogen atom, add halogenating agent.As concrete method, at first will by formula (1) to formula (4) represented and R be that the compound dissolution of hydrogen atom is in tetrahydrofuran (THF) (THF) equal solvent.Add for example n-BuLi (n-Butyl Lithium) therein, further splash into the solution that in THF, is dissolved with halogenating agents such as dibromo tetrachloroethane, obtain target compound.
Among this preparation method, by being to add n-BuLi in the compound of hydrogen atom at represented by above-mentioned formula (1) and R, the hydrogen that is combined on the carbon atom adjacent with sulphur or selenium is removed, generate lithium salts to formula (4).By making the reaction of this lithium salts and halogenating agent, make matrix generation halogenation.Then, by for example filter to wait the solids constituent that will separate out from, obtain by formula (5) to the represented compound of formula (8).
Among this preparation method,, can use bromizating agent or iodinating agent as halogenating agent.As bromizating agent, can suitably use dibromo tetrachloroethane, bromine, pyridinium bromide perbromide, the amino tribromide of tetraalkyl etc., as iodinating agent, can suitably use iodine, ethylidene periodide, iodate perflexane, the amino triiodide of tetraalkyl etc.
With respect to being the compound of hydrogen atom by formula (1) to the R in the formula (4), n-BuLi can add more than 2 equivalents at least.This is because can obtain the compound as target more efficiently by 2 removals in the hydrogen atom that formula (1) is contained to the represented compound of formula (4).And want under the situation that reaction is slow, the side reaction probability is little between the position beyond the position that replaces, perhaps by formula (1) to the situation that solvability low, reaction be difficult to carry out of the represented compound of formula (4) for solvent, can also further add superfluous n-BuLi.
Can recently add halogenating agent with the mole more than the n-BuLi that adds.As their proportioning, for example with respect to 1 mole by formula (1) to the represented compound of formula (4), can add n-BuLi, about 10 moles with about 3～5 moles and add halogenating agent.
Reaction times can be about 30 minutes～1 hour.Even less than 30 minutes, so long as can make the time of removing the reaction end of hydrogen by n-BuLi, some also are fine than above-mentioned reaction times weak point.
In addition, among this preparation method, example carry out halogenated example by the halogen-lithium exchange reactions that uses n-BuLi, but halogenated method is not limited thereto.Can compatibly adopt the known method such as method of using other proton removers.
Organic semiconductor material
Then, the embodiment to organic semiconductor material of the present invention describes.Organic semiconductor material of the present invention is characterised in that, contains more than one by above-mentioned formula (1), formula (2), formula (3) or the represented compound of formula (4).
Have naphthalene-thiophene skeleton or naphthalene-selenium phenol skeleton by formula (1), formula (2), formula (3) or the represented compound of formula (4).This compound is because the interaction of π track and have conjugated system at each intramolecularly, and demonstrate by the sulphur atom that in the thiphene ring of each molecule or selenium phenol ring, contains or selenium atom produce intermolecular than strong interaction.Therefore, can carry out mobility of charge carrier effectively.Its result because compound of the present invention has good electric field mobility, can be used to as organic semiconductor material.
Organic semiconductor material can only contain by formula (1) a kind to the represented compound of formula (4), also can contain these compounds more than 2 kinds.In addition, not hindering by formula (1) to the limit of the characteristic of the represented compound of formula (4), can also contain other materials.In addition, also can regulate electric field mobility by known method impurity.
Organic semiconductor device
Then, the embodiment to organic semiconductor device of the present invention describes.The feature of organic semiconductor device of the present invention is, uses the organic semiconductor material that contains more than at least a kind by the represented compound of above-mentioned formula (1), formula (2), formula (3) or formula (4).Such organic semiconductor device comprises the thin film transistor that for example has organic semiconductor layer, has organic charge carrier transport layer or luminescent layer or has the light-emitting device of said two devices concurrently.
In the organic semiconductor device of the present invention, except the organic semiconductor material that uses the invention described above, can adopt known material and structure, have no particular limits.
Preparation method for organic semiconductor device is not particularly limited, and can adopt known in the past various preparation methods.Need to prove, adopting coating method to compare under the situation of difficult, preferably wait to prepare by vacuum vapour deposition because the solvability of organic semiconductor material is lower slightly.
In the organic semiconductor device of the present invention owing to use organic semiconductor material of the present invention to come substituted for silicon, thereby no longer need be when using silicon the technology of necessary consuming cost, therefore, can prepare semiconductor device at an easy rate.
In addition, owing to use organic semiconductor material, compare mechanical flexibility excellence, and light weight with the device that uses silicon.Therefore, can be applied to the display unit, intelligent label etc. of light weight.
Embodiment
Below, to compound of the present invention and preparation method thereof, be described more specifically by providing embodiment.
Embodiment 1
To describing by represented the synthetic of the compound with linearity skeleton of formula (1).Need to prove, the structure of compound be by 1H NMR ( 1The H nuclear magnetic resonance spectrum), EIMS (mass analysis spectrum) and determine.The employed machine of the mensuration of each spectral line is as follows.
1H-NMR:JEOL Lambda 400 spectrographs
: JEOL EX-270 spectrograph
EIMS：Shimadzu?QP-5050A
In addition, these machines use in other embodiment described later similarly.
For synthesizing of naphthalene [2,3-b:6,7-b '] two thiophene, sequentially describe.
1,3,5,7-tetrabromobisphenol, 6-dihydroxy naphthlene synthetic
With 2, (2g 12.5mol) is dissolved in the acetic acid (60ml) the 6-dihydroxy naphthlene.Here, use acetic acid as solvent.(2.6ml, 50.7mol), (120 ℃～125 ℃) react under reflux temperature to splash into bromine in this solution.
As described in the embodiment of invention, in this stage, with 2, reactive high 1 and 5 hydrogen atom in the hydrogen atom that contains in the 6-dihydroxy naphthlene are replaced by bromine atoms, and stop at generation 1,5-two bromo-2,6-dihydroxy naphthlene.For final naphthalene two thiophene that obtain to have the linearity skeleton, 3 and 7 s' hydrogen atom is replaced by bromine.
Then, in this reaction solution further totally 5 dripping bromine and each dripping bromine (2.6ml), (50mg 1.3mol), carries out 76 hours reaction to add iron powder as catalyzer.
Then, this reaction solution is cooled to room temperature, adds pure water (50ml).Filter and take out the solid of separating out.With acetone this solid is cleaned, drying under reduced pressure obtains thick resultant.
Use 1, the 4-diox is that solvent carries out recrystallize, refining to the thick resultant that obtains.Obtain 1,3,5 of colourless needle crystal, 7-tetrabromobisphenol, 6-dihydroxy naphthlene (3.0g, yield 51%).
As mentioned above, by bromine being dripped several times and adding iron powder, can synthesize 1,3,5 with high yield, 7-tetrabromobisphenol, 6-dihydroxy naphthlene as catalyzer.
The reaction formula of above-mentioned reaction is as follows.
Figure BPA00001373358600111
1,3,5 of gained, the 7-tetrabromobisphenol, the various spectrum data of 6-dihydroxy naphthlene are as follows.
1H-NMR(270MHz，CDCl 3)δ6.18(s，2H，OH)，8.31(s，2H，ArH)；EIMS(70eV)m/z＝476(M +)
3,7-two bromo-2,6-dihydroxy naphthlene synthetic
With 1,3,5, the 7-tetrabromobisphenol, (1.0g 2.1mmol) is dissolved in acetic acid (20ml) to the 6-dihydroxy naphthlene.Wherein add spongy tin (broken laminar tin) (499mg, 4.2mmol) after, under reflux temperature, stirred 62 hours, react.
Reaction solution is cooled to room temperature, adds pure water (20ml).Filter and take out the solid of separating out.By to this solid drying under reduced pressure, obtain 3 of white solid, 7-two bromo-2,6-dihydroxy naphthlene (530mg, 79%).
The reaction formula of above-mentioned reaction is as follows.
Figure BPA00001373358600121
3 of gained, 7-two bromo-2, the various spectrum data of 6-dihydroxy naphthlene are as follows.
1H-NMR(400MHz，CDCl 3)δ5.58(s，2H，OH)，7.25(s，2H，ArH)，7.89(s，2H，ArH)；EIMS(70eV)m/z＝318(M +)
3,7-two bromo-2, two (trifluoromethane sulphonyl) naphthalenes of 6-synthetic
Under nitrogen atmosphere, with 3,7-two bromo-2, the 6-dihydroxy naphthlene (636mg, 2.0mmol) and pyridine (1.0ml 12mmol) is dissolved in the methylene dichloride (20ml).
Under ice bath, in this solution, add lentamente Trifluoromethanesulfonic anhydride (0.7ml, 4.4mmol).It after 15 hours, is added pure water (10ml) and 1N hydrochloric acid (10ml) in stirring at room.
Then, by methylene dichloride (20ml) this reaction soln is extracted.Should extract and carry out in the same way 3 times.Afterwards, clean organic phase with saturated aqueous common salt (20ml).Should clean and carry out in the same way 3 times.
After with anhydrous magnesium sulfate the water that is contained in the organic phase being removed, under reduced pressure make solvent evaporation, obtain thick resultant.By with the methylene dichloride being the silica gel column chromatography (Rf=0.95 of target compound of migration phase.In addition, below if no special instructions, Rf represents the Rf value of the target compound in the condition of each silica gel column chromatography.) this thick resultant is carried out separation and purification, obtain 3 of white solid thus, 7-two bromo-2, two (trifluoromethane sulphonyl) naphthalenes (970mg, yield 84%) of 6-.
The reaction formula of above-mentioned reaction is as follows.
Figure BPA00001373358600122
3 of gained, 7-two bromo-2, the various spectrum data of two (trifluoromethane sulphonyl) naphthalenes of 6-are as follows.
1H-NMR(270MHz，CDCl 3)δ7.14(s，2H，ArH)，8.25(s，2H，ArH)；EIMS(70eV)m/z＝582(M +)
2,6-two bromo-3, two (trimethylsilyl acetylene) naphthalenes of 7-synthetic
Under nitrogen atmosphere, with 3,7-two bromo-2, (582mg 1.0mmol) is dissolved in DMF (7ml) and the Diisopropylamine (7ml) two (trifluoromethane sulphonyl) naphthalenes of 6-.This solution is carried out the degassing in 30 minutes.
In this solution, add Pd (PPh as catalyzer 3) 2Cl 2(70mg, 0.05mmol, 10mol%) and CuI (38mg, 0.1mmol, 20mol%) and as the trimethylsilyl acetylene of reagent (0.28ml, 2.0mmol).After it is at room temperature stirred 11 hours, add pure water (1ml) and 1N hydrochloric acid (1ml), make to react to stop.
(5ml) extracts this reaction solution with methylene dichloride.This extraction is carried out 3 times in an identical manner.After the extraction, use saturated aqueous common salt (5ml) to clean organic phase.Should clean and carry out in an identical manner 3 times.
After using anhydrous magnesium sulfate that the water that contains in the organic phase is removed, under reduced pressure make solvent evaporation, obtain thick resultant.By being that the silica gel column chromatography (Rf=0.2) that moves phase carries out separation and purification to this thick resultant with the normal hexane, obtain 2 of white solid, 6-two bromo-3, two (trimethylsilyl acetylene) naphthalenes (162mg, yield 34%) of 7-.
The reaction formula of above-mentioned reaction is as follows.
Figure BPA00001373358600131
2 of gained, 6-two bromo-3, the various spectrum data of two (trimethylsilyl acetylene) naphthalenes of 7-are as follows.
1H-NMR(270MHz，CDCl 3)δ0.29(s，18H，TMS)，7.87(s，2H，ArH)，7.97(s，2H，ArH)；EIMS(70eV)m/z＝478(M +)
Synthesizing of naphthalene [2,3-b:6,7-b '] two thiophene
Under nitrogen atmosphere, make Na 2S9H 2O (101mg, 0.42mmol) outstanding turbid in N-N-methyl-2-2-pyrrolidone N-(NMP) (3ml) in, stirred 15 minutes.
In this suspension liquid, add 2,6-two bromo-3, (50mg 0.1mmol), stirred 10 hours down at 190 ℃ two (trimethylsilyl acetylene) naphthalenes of 7-.
Then, it is cooled to room temperature after, be injected in the saturated aqueous ammonium chloride (20ml).With solid filtering, the taking-up of separating out.
By being that the silica gel column chromatography (Rf=0.95) that moves phase carries out separation and purification to this solid with the normal hexane, obtain naphthalene [2,3-b:6,7-b '] two thiophene (26mg, yield 100%) of orange solids.
The reaction formula of above-mentioned reaction is as follows.
Figure BPA00001373358600132
The various spectrum data of the naphthalene of gained [2,3-b:6,7-b '] two thiophene are as follows.
1H-NMR(270MHz，CDCl 3)δ7.43(d，2H，J＝5.8Hz，ArH)，7.51(d，2H，J＝5.8Hz，ArH)，8.41(s，2H，ArH)，8.52(s，2H，ArH)；EIMS(70eV)m/z＝240(M +)；mp＞300℃
Embodiment 2
Then, for 2, the synthetic order of 7-hexichol naphthalene [2,3-b:6,7-b '] two thiophene describes.
2,6-two bromo-3, two (phenylacetylene) naphthalenes of 7-synthetic
Use by aforesaid method synthetic 3,7-two bromo-2, two (trifluoromethane sulphonyl) naphthalenes of 6-come Synthetic 2 by the following method, 6-two bromo-3, two (phenylacetylene) naphthalenes of 7-.
Under nitrogen atmosphere, with 3,7-two bromo-2, (582mg 1.0mmol) is dissolved in DMF (7ml) and Diisopropylamine (7ml) to two (trifluoromethane sulphonyl) naphthalenes of 6-.This solution is carried out the degassing in 30 minutes.
In this solution, add Pd (PPh as catalyzer 3) 2Cl 2(70mg, 0.05mmol, 10mol%) and CuI (20mol%) and as the phenylacetylene of reagent (0.22ml 2.0mmol), at room temperature stirs and reacted in 11 hours for 38mg, 0.1mmol.Afterwards, add pure water (1ml) and 1N hydrochloric acid (1ml), reaction is stopped.
Use methylene dichloride (5ml) that this reaction solution is extracted.This extraction is adopted and is carried out in the same way 3 times.After the extraction, use saturated aqueous common salt (5ml) to clean organic phase.Should clean to adopt and carry out in the same way 3 times.
After using anhydrous magnesium sulfate that the water that contains in the organic phase is removed, under reduced pressure make solvent evaporation, obtain thick resultant.
By being that the silica gel column chromatography (Rf=0.1) that moves phase carries out separation and purification to this thick resultant with the normal hexane, obtain 2 of white solid, 6-two bromo-3, two (phenylacetylene) naphthalenes (397mg, yield 82%) of 7-.
The reaction formula of above-mentioned reaction is as follows.
2 of gained, 6-two bromo-3, the various spectrum data of two (phenylacetylene) naphthalenes of 7-are as follows.
1H-NMR(400MHz，CDCl 3)δ7.39-7.41(m，6H，ArH)，7.62-7.64(m，4H，ArH)，7.97(s，2H，ArH)，8.07(s，2H，ArH)；EIMS(70eV)m/z＝486(M +)
2,7-hexichol naphthalene [2,3-b:6,7-b '] two thiophene synthetic
Under nitrogen atmosphere, make Na 2S9H 2O (202mg, 0.42mmol) outstanding turbid in NMP (3ml), stirred 15 minutes.
In this suspension liquid, add 2 of previous gained, 6-two bromo-3, (100mg 0.2mmol), stirred 10 hours at 190 ℃ two (phenylacetylene) naphthalenes of 7-.
After this reaction solution is cooled to room temperature, be injected in the saturated aqueous ammonium chloride (20ml).Filtering and take out the yellow solid (75mg, yield 96%) of separating out carries out.
By this yellow solid is carried out sublimation purifying, obtain 2,7-hexichol naphthalene [2,3-b:6,7-b '] two thiophene (25mg, yield 32%).
The reaction formula of above-mentioned reaction is as follows.
Figure BPA00001373358600151
2 of gained, the spectrum data of 7-hexichol naphthalene [2,3-b:6,7-b '] two thiophene are as follows.Need to prove, because 2,7-hexichol naphthalene [2,3-b:6,7-b '] two thiophene are insolublies, therefore can't carry out 1H-NMR measures.
EIMS(70eV)m/z＝392(M +)
Embodiment 3
Then, to 2, the synthetic of 7-dioctyl naphthalene [2,3-b:6,7-b '] two thiophene sequentially describes.
2,6-two bromo-3,7-two (decine-1-yl) naphthalene synthetic
Use is by preceding method synthetic 2,6-two bromo-3, two (trifluoromethane sulphonyl) naphthalenes of 7-, Synthetic 2 by the following method, 6-two bromo-3,7-two (decine-1-yl) naphthalene.
Under nitrogen atmosphere, with 2,6-two bromo-3, two (trifluoromethane sulphonyl) naphthalenes of 7-(493mg, 1.0mmol) be dissolved in DMF (10ml) and Diisopropylamine (0.42ml, 3.0mmol) in.This solution is carried out the degassing in 30 minutes.
In this solution, add Pd (PPh as catalyzer 3) 2Cl 2(70mg, 0.1mmol, 10mol%) and CuI (20mol%) and as the 1-decine of reagent (0.54ml 3.0mmol), at room temperature stirs and reacted in 27 hours for 38mg, 0.1mmol.Afterwards, add pure water (1ml) and 1N hydrochloric acid (1ml), reaction is stopped.
Use methylene dichloride (10ml) that this reaction solution is extracted.This extraction is carried out 3 times in an identical manner.After the extraction, use saturated aqueous common salt (10ml) that organic phase is cleaned.Should clean and carry out in an identical manner 3 times.
After using anhydrous magnesium sulfate that the moisture that contains in the organic phase is removed, under reduced pressure make solvent evaporation, obtain thick resultant.
By being that the silica gel column chromatography (Rf=0.3) that moves phase carries out separation and purification to this thick resultant with the normal hexane, obtain 2 of white solid, 6-two bromo-3,7-two (decine-1-yl) naphthalene (488mg, yield 87%).
The reaction formula of above-mentioned reaction is as follows.
Figure BPA00001373358600152
2 of gained, 6-two bromo-3, the various spectrum data of 7-two (decine-1-yl) naphthalene are as follows.
1H-NMR(270MHz，CDCl 3)δ0.89(t，6H，J＝7.02Hz，CH 2)，1.27-1.37(m，20H，CH 2)，1.61-1.72(m，4H，CH 2)，2.51(t，4H，J＝6.62Hz，CH 2)，7.79(s，2H，ArH)，7.95(s，2H，ArH)；EIMS(70eV)m/z＝558(M +)
2,7-dioctyl naphthalene [2,3-b:6,7-b '] two thiophene synthetic
Under nitrogen atmosphere, make Na 2S9H 2O (346mg, 1.44mmol) outstanding turbid in NMP (12ml), stirred 15 minutes.
In this suspension liquid, add 2 of gained, 6-two bromo-3, (200mg 0.36mmol), stirred 9 hours down at 190 ℃ 7-two (decine-1-yl) naphthalene.
After this reaction solution is cooled to room temperature, be injected in the saturated aqueous ammonium chloride (30ml).Filter and take out the solid of separating out.
By being the silica gel column chromatography (Rf=0.95) of migration phase with the methylene dichloride and using the recrystallize of chloroform as solvent, this solid is carried out separation and purification, obtain 2 of yellow needle crystal, 7-dioctyl naphthalene [2,3-b:6,7-b '] two thiophene (130mg, yield 78%).
The reaction formula of above-mentioned reaction is as follows.
Figure BPA00001373358600161
2 of gained, the various spectrum data of 7-dioctyl naphthalene [2,3-b:6,7-b '] two thiophene are as follows.
1H-NMR(400MHz，CDCl 3)δ0.89(t，6H，J＝7.4Hz，CH 2)，1.28-1.50(m，20H，CH 2)，1.75-1.83(m，4H，CH 2)，2.92(t，4H，J＝7.4Hz，CH 2)，7.06(s，2H，ArH)，8.16(s，2H，ArH)，8.32(s，2H，ArH)；EIMS(70eV)m/z＝464(M +)；mp?269-271℃
Embodiment 4
Then, based on embodiment the synthesis example by the represented compound of formula (2) is specifically described.
At first, for 2,7-hexichol naphthalene [2,3-b:7,6-b '] two thiophene synthetic below sequentially describes.
1,3,6-three bromo-2,7 dihydroxy naphthalenes synthetic
Under nitrogen atmosphere, (5g 31mmol) is dissolved in acetic acid (150ml) with 2,7 dihydroxy naphthalene.Need to prove that the acetic acid here uses as solvent.
(5.3ml, 103mmol), reaction is 41 hours under reflux temperature for dripping bromine in this solution.
After this reaction solution is cooled to room temperature, add pure water (50ml).Filter and take out the solid of separating out.By pure water solid is cleaned, by drying under reduced pressure, obtained 1,3 of white solid, 6-three bromo-2,7 dihydroxy naphthalenes (10g, yield 83%).
The reaction formula of above-mentioned reaction is as follows.
Figure BPA00001373358600162
1,3 of gained, the various spectrum data of 6-three bromo-2,7 dihydroxy naphthalenes are as follows.
1H-NMR(270MHz，CDCl 3)δ5.88(s，1H，OH)，6.24(s，1H，OH)，7.60(s，1H，ArH)，7.88(s，1H，ArH)，7.89(s，1H，ArH)；EIMS(70eV)m/z＝396(M +)
3,6-two bromo-2,7 dihydroxy naphthalenes synthetic
Make 1,3, (5.0g 12.6mmol) is dissolved in acetic acid (20ml) to 6-three bromo-2,7 dihydroxy naphthalenes.In this solution, add spongy tin (laminar tin) (1.6g, 12.6mmol) after, under reflux temperature, stirred 120 hours.
After this reaction solution is cooled to room temperature, add pure water (100ml).Filter and take out the solid of separating out.Under reduced pressure, obtain 3 of white solid, 6-two bromo-2,7 dihydroxy naphthalenes (3.4g, yield 85%) with this solid drying.
The reaction formula of above-mentioned reaction is as follows.
Figure BPA00001373358600171
3 of gained, the various spectrum data of 6-two bromo-2,7 dihydroxy naphthalenes are as follows.
1H-NMR(270MHz，CDCl 3)δ5.67(s，2H，OH)，7.24(s，2H，ArH)，7.87(s，2H，ArH)；EIMS(70eV)m/z＝318(M +)
3,6-two bromo-2, two (trifluoromethane sulphonyl) naphthalenes of 7-synthetic
With 3 of gained, 6-two bromo-2,7 dihydroxy naphthalenes (3.0g, 9.4mmol) under nitrogen atmosphere, be dissolved in pyridine (4.5ml, 56mmol) and methylene dichloride (90ml).
Under ice bath, in this solution, slowly add Trifluoromethanesulfonic anhydride (3.3ml, 21mmol).After at room temperature stirring 4 hours, add pure water (10ml) and 1N hydrochloric acid (10ml), reaction is stopped.
Then, use methylene dichloride (20ml) that this reaction solution is extracted.This extraction is carried out 3 times in the same way.Afterwards, with saturated aqueous common salt (20ml) organic phase is cleaned.Should clean and carry out in the same way 3 times.
Then, after the use anhydrous magnesium sulfate is removed the moisture that contains in the organic phase, under reduced pressure make solvent evaporation, obtain thick resultant.By being that the silica gel column chromatography (Rf=0.95) that moves phase carries out separation and purification to this thick resultant with the methylene dichloride, obtain 3 of white solid, 6-two bromo-2, two (trifluoromethane sulphonyl) naphthalenes (3.3g, yield 60%) of 7-.
The reaction formula of above-mentioned reaction is as follows.
3 of gained, 6-two bromo-2, the various spectrum data of two (trifluoromethane sulphonyl) naphthalenes of 7-are as follows.
1H-NMR(400MHz，CDCl 3)δ7.86(s，2H，ArH)，8.19(s，2H，ArH)；EIMS(70eV)m/z＝582(M +)
3,6-two bromo-2, two (phenylacetylene) naphthalenes of 7-synthetic
Under nitrogen atmosphere, with 3,6-two bromo-2, (582mg 1.0mmol) is dissolved in DMF (7ml) and Diisopropylamine (7ml) to two (trifluoromethane sulphonyl) naphthalenes of 7-.This solution is carried out the degassing in 30 minutes.
In this solution, add Pd (PPh as catalyzer 3) 2Cl 2(70mg, 0.05mmol, 10mol%) and CuI (38mg, 0.1mmol, 20mol%) and as the phenylacetylene of reagent (0.22ml, 2.0mmol).At room temperature stir made its reaction in 11 hours after, add pure water (1ml) and 1N hydrochloric acid (1ml), make to react to stop.
Then, use methylene dichloride (5ml) that this reaction solution is extracted.This extraction is carried out 3 times in the same way.After the extraction, use saturated aqueous common salt (5ml) to clean organic phase.Should clean and carry out in the same way 3 times.
After using anhydrous magnesium sulfate that the moisture that contains in the organic phase is removed, under reduced pressure make solvent evaporation, obtain thick resultant.
By being that the silica gel column chromatography (Rf=0.1) that moves phase carries out separation and purification to this thick resultant with the normal hexane, obtain 3 of white solid, 6-two bromo-2, two (phenylacetylene) naphthalenes (243mg, yield 50%) of 7-.
The reaction formula of above-mentioned reaction is as follows.
Figure BPA00001373358600181
3 of gained, 6-two bromo-2, the various spectrum data of two (phenylacetylene) naphthalenes of 7-are as follows.
1H-NMR(270MHz，CDCl 3)δ7.38-7.42(m，6H，ArH)，7.62-7.65(m，4H，ArH)，8.01(s，2H，ArH)，8.03(s，2H，ArH)；EIMS(70eV)m/z＝486(M +)
2,7-hexichol naphthalene [2,3-b:7,6-b '] two thiophene synthetic
Under nitrogen atmosphere, make Na 2S9H 2O (404mg, 1.68mmol) outstanding turbid in NMP (12ml), stirred 15 minutes.
In this suspension liquid, add 3,6-two bromo-2, (200mg 0.4mmol), stirred 14 hours down at 190 ℃ two (phenylacetylene) naphthalenes of 7-.
After this reaction solution is cooled to room temperature, be injected in the saturated aqueous ammonium chloride (20ml).Filter and take out the solid of separating out.
This solid is cleaned by pure water, ethanol, normal hexane, methylene dichloride, hot chloroform, obtained 2,7-hexichol naphthalene [2,3-b:7,6-b '] two thiophene (73mg, yield 45%).
The reaction formula of above-mentioned reaction is as follows.
Figure BPA00001373358600182
2 of gained, the spectrum data of 7-hexichol naphthalene [2,3-b:7,6-b '] two thiophene are as follows.Need to prove, because 2,7-hexichol naphthalene [2,3-b:7,6-b '] two thiophene are insolublies, can't carry out NMR and measure.
EIMS(70eV)m/z＝392(M +)
Embodiment 5
Then, for 2,7-dioctyl naphthalene [2,3-b:7,6-b '] two thiophene synthetic below sequentially describes.
3,6-two bromo-2,7-two (decine-1-yl) naphthalene synthetic
Use synthetic 3 as previously mentioned, 6-two bromo-2, two (trifluoromethane sulphonyl) naphthalenes of 7-synthesize 3 by following mode, 6-two bromo-2,7-two (decine-1-yl) naphthalene.
Under nitrogen atmosphere, with 3,6-two bromo-2, (582mg 1.0mmol) is dissolved in DMF (7ml) and the Diisopropylamine (7ml) two (trifluoromethane sulphonyl) naphthalenes of 7-.This solution is carried out the degassing in 30 minutes.
In this solution, add Pd (PPh as catalyzer 3) 2Cl 2(70mg, 0.05mmol, 10mol%) and CuI (38mg, 0.1mmol, 20mol%) and as the 1-decine of reagent (0.36ml, 2.0mmol).After stirring at room made its reaction in 11 hours, add pure water (1ml) and 1N hydrochloric acid (1ml) reaction is stopped.
Use methylene dichloride (5ml) that this reaction solution is extracted.This extraction is carried out 3 times in the same way.The extraction back uses saturated aqueous common salt (5ml) to clean organic phase.Should clean and carry out in the same way 3 times.
After using anhydrous magnesium sulfate that the moisture that contains in the organic phase is removed, under reduced pressure make solvent evaporation, obtain thick resultant.
By being that the silica gel column chromatography (Rf=0.3) that moves phase carries out separation and purification to this thick resultant with the normal hexane, obtain 3 of white solid, 6-two bromo-2,7-two (decine-1-yl) naphthalene (444mg, yield 80%).
The reaction formula of above-mentioned reaction is as follows.
Figure BPA00001373358600191
3 of gained, 6-two bromo-2, the various spectrum data of 7-two (decine-1-yl) naphthalene are as follows.
1H-NMR(270MHz，CDCl 3)δ0.89(t，6H，J＝6.8Hz，CH 2)，1.27-1.72(m，24H，CH 2)，2.50(t，4H，J＝6.9Hz，CH 2)，7.81(s，2H，ArH)，7.93(s，2H，ArH)，EIMS(70eV)m/z＝558(M +)
2,7-dioctyl naphthalene [2,3-b:7,6-b '] two thiophene synthetic
Under nitrogen atmosphere, make Na 2S9H 2O (346mg, 1.44mmol) outstanding turbid in NMP (12ml), stirred 15 minutes.
In this suspension liquid, add 3,6-two bromo-2, (200mg 0.36mmol), stirred 12 hours down at 190 ℃ 7-two (decine-1-yl) naphthalene.Then, this reaction solution is cooled to room temperature after, be injected in the saturated aqueous ammonium chloride (30ml).To filter and take out the solid of separating out.
This solid is cleaned with pure water, ethanol, obtained 2 of faint yellow solid, 7-dioctyl naphthalene [2,3-b:7,6-b '] two thiophene (168mg, yield 100%).
The reaction formula of above-mentioned reaction is as follows.
Figure BPA00001373358600201
2 of gained, the various spectrum data of 7-dioctyl naphthalene [2,3-b:7,6-b '] two thiophene are as follows.
1H-NMR(400MHz，CDCl 3)δ0.88(t，6H，J＝7.0Hz，CH 3)，1.28-1.81(m，24H，CH 2)，2.92(t，4H，J＝7.3Hz，CH 2)，7.05(s，2H，ArH)，8.21(s，2H，ArH)，8.26(s，2H，ArH)；EIMS(70eV)m/z＝464(M +)
Embodiment 6
Then, synthetic for naphthalene [2,3-b:7,6-b '] two thiophene below sequentially describes.
3,6-two bromo-2, two (trimethylsilyl acetylene) naphthalenes of 7-synthetic
Use synthetic 3 as previously mentioned, 6-two bromo-2, two (trifluoromethane sulphonyl) naphthalenes of 7-synthesize 3 by following mode, 6-two bromo-2, two (trimethylsilyl acetylene) naphthalenes of 7-.
Under nitrogen atmosphere with 3,6-two bromo-2, (582mg 1.0mmol) is dissolved in DMF (7ml) and Diisopropylamine (7ml) to two (trifluoromethane sulphonyl) naphthalenes of 7-.This solution is carried out the degassing in 30 minutes.
In this solution, add Pd (PPh as catalyzer 3) 2Cl 2(70mg, 0.05mmol, 10mol%) and CuI (38mg, 0.1mmol, 20mol%) and as the trimethylsilyl acetylene of reagent (0.22ml, 2.0mmol).At room temperature stir and reacted in 11 hours, add pure water (1ml), normal hexane (20ml).Then by removing by filter insoluble solid.At this moment, use " Ha イ Off ロ ス one パ one セ Le " (registered trademark) as filtration adjuvant.
Use normal hexane (5ml) that this filtrate is extracted.This extraction is carried out 3 times in the same way.After the extraction, use saturated aqueous common salt (5ml) to clean organic phase.Should clean and carry out in the same way 3 times.
After using anhydrous magnesium sulfate that the moisture content that contains in the organic phase is removed, under reduced pressure make solvent evaporation, obtain thick resultant.
By being that the silica gel column chromatography (Rf=0.2) that moves phase carries out separation and purification to this thick resultant with the normal hexane, obtain 3 of white solid, 6-two bromo-2, two (trimethylsilyl acetylene) naphthalenes (92mg, yield 19%) of 7-.
The reaction formula of above-mentioned reaction is as follows.
Figure BPA00001373358600202
3 of gained, 6-two bromo-2, the various spectrum data of two (trimethylsilyl acetylene) naphthalenes of 7-are as follows.
1H-NMR(270MHz，CDCl 3)δ0.30(s，18H，TMS)，7.90(s，2H，ArH)，7.95(s，2H，ArH)；EIMS(70eV)m/z＝478(M +)
Synthesizing of naphthalene [2,3-b:7,6-b '] two thiophene
Under nitrogen atmosphere, make Na 2S9H 2O (101mg, 0.42mmol) outstanding turbid in NMP (3ml), stirred 15 minutes.
In this suspension liquid, add 3,6-two bromo-2, (50mg 0.10mmol), stirred 12 hours down at 190 ℃ two (trimethylsilyl acetylene) naphthalenes of 7-.After it is cooled to room temperature, be injected in the saturated aqueous ammonium chloride (20ml).Filter and take out the solid of separating out.
This solid is cleaned with pure water, ethanol, normal hexane, obtained naphthalene [2,3-b:7,6-b '] two thiophene (73mg, yield 45%) of yellow solid.
The reaction formula of above-mentioned reaction is as follows.
Figure BPA00001373358600211
The various spectrum data of the naphthalene of gained [2,3-b:7,6-b '] two thiophene are as follows.
1H-NMR(270MHz，CDCl 3)δ7.43(d，2H，J＝5.5Hz，ArH)，7.50(d，2H，J＝5.5Hz?ArH)，8.45(s，2H，ArH)，8.47(s，2H，ArH)；EIMS(70eV)m/z＝240(M +)
Embodiment 7
Then, based on embodiment the synthesis example by the represented compound of formula (3) is specifically described.
At first, synthetic about naphthalene [1,2-b:5,6-b '] two thiophene below sequentially describes.
1,5-two chloro-2,6-dihydroxy naphthlene synthetic
Under nitrogen atmosphere, with 2, (3.0g 18.7mmol) is dissolved in the acetic acid (90ml) the 6-dihydroxy naphthlene.Need explanation to be, the acetic acid here is as solvent.
(3.0ml 37.5mmol), at room temperature stirred 5 hours to splash into sulfuryl chloride in this solution.Then, in reaction solution, add pure water (50ml).Filter and take out the solid of separating out.Under reduced pressure, obtain 1 of white solid, 5-two chloro-2,6-dihydroxy naphthlene (3.3g, yield 78%) with this solid drying.
The reaction formula of above-mentioned reaction is as follows.
Figure BPA00001373358600212
1 of gained, 5-two chloro-2, the various spectrum data of 6-dihydroxy naphthlene are as follows.
1H-NMR(270MHz，CDCl 3)δ5.79(s，2H，OH)，7.35(d，2H，J＝8.9Hz，ArH)，7.96(d，2H，J＝8.9Hz，ArH)；EIMS(70eV)m/z＝228(M +)
1,5-two chloro-2, two (trifluoromethane sulphonyl) naphthalenes of 6-synthetic
Under nitrogen atmosphere, with 1,5-two chloro-2, the 6-dihydroxy naphthlene (2.3g, 10mmol) and pyridine (4.8ml 60mmol) is dissolved in methylene dichloride (100ml).Need to prove that pyridine is an additive of not wanting thing as removing, methylene dichloride is as solvent.
Under ice bath, in this solution, slowly add Trifluoromethanesulfonic anhydride (3.6ml, 22mmol).After it is at room temperature stirred 18 hours, add pure water (10ml) and 1N hydrochloric acid (10ml), make to react to stop.
Then, use methylene dichloride (20ml) that this reaction solution is extracted.This extraction is carried out 3 times in an identical manner.After the extraction, organic phase is cleaned with saturated aqueous common salt (20ml).Should clean and carry out in an identical manner 3 times.
After using anhydrous magnesium sulfate that the moisture that contains in the organic layer is removed, under reduced pressure make solvent evaporation, obtain thick resultant.
By being that the silica gel column chromatography (Rf=0.95) that moves phase carries out separation and purification to this thick resultant with the methylene dichloride, obtain 1 of white solid, 5-two chloro-2, two (trifluoromethane sulphonyl) naphthalenes (4.9g, yield 99%) of 6-.
The reaction formula of above-mentioned reaction is as follows.
1 of gained, 5-two chloro-2, the various spectrum data of two (trifluoromethane sulphonyl) naphthalenes of 6-are as follows.
1H-NMR(270MHz，CDCl 3)δ7.68(d，2H，J＝9.3Hz，ArH)，8.40(d，2H，J＝9.3Hz，ArH)；EIMS(70eV)m/z＝492(M +)
1,5-two chloro-2, two (trimethylsilyl acetylene) naphthalenes of 6-synthetic
Under nitrogen atmosphere, with 1,5-two chloro-2, two (trifluoromethane sulphonyl) naphthalenes of 6-(247mg, 0.5mmol) and triethylamine (0.21ml 1.5mmol) is dissolved among the DMF (5ml).This solution is carried out the degassing in 30 minutes.
In this solution, add Pd (PPh as catalyzer 3) 2Cl 2(35mg, 0.05mmol, 10mol%) and CuI (19mg, 0.1mmol, 20mol%) and as the trimethylsilyl acetylene of reagent (0.21ml, 15mmol).After it is at room temperature stirred 17 hours 30 minutes, add pure water (1ml) and 1N hydrochloric acid (1ml), make to react to stop.
Use methylene dichloride (5ml) that this reaction solution is extracted.This extraction is carried out 3 times in the same way.After the extraction, use saturated aqueous common salt (5ml) that organic phase is cleaned.Should clean and carry out in the same way 3 times.
After using anhydrous magnesium sulfate that the moisture that contains in the organic phase is removed,, obtain thick resultant with the solvent vapourisation under reduced pressure.
By being that the silica gel column chromatography (Rf=0.2) that moves phase carries out separation and purification to this thick resultant with the normal hexane, obtain 1 of white solid, 5-two chloro-2, two (trimethylsilyl acetylene) naphthalenes (89mg, 46%) of 6-.
The reaction formula of above-mentioned reaction is as follows.
Figure BPA00001373358600231
1 of gained, 5-two chloro-2, the various spectrum data of two (trimethylsilyl acetylene) naphthalenes of 6-are as follows.
1H-NMR(270MHz，CDCl 3)δ0.31(s，18H，TMS)，7.61(d，2H，J＝8.8Hz，ArH)，8.12(d，2H，J＝8.8Hz，ArH)；EIMS(70eV)m/z＝388(M +)
Synthesizing of naphthalene [1,2-b:5,6-b '] two thiophene
Under nitrogen atmosphere, make Na 2S9H 2O (615mg, 2.56mmol) outstanding turbid in NMP (15ml), stirred 15 minutes.
In this suspension liquid, add 1,5-two chloro-2, (250mg 0.64mmol), stirred 12 hours down at 190 ℃ two (trimethylsilyl acetylene) naphthalenes of 6-.After it is cooled to room temperature, be injected in the saturated aqueous ammonium chloride (50ml).Filter and take out the solid of separating out.
By being that the silica gel column chromatography (Rf=0.2) that moves phase carries out separation and purification to this solid with the normal hexane, obtain naphthalene [1,2-b:5,6-b '] two thiophene (139mg, 90%) of white solid.
The reaction formula of above-mentioned reaction is as follows.
Figure BPA00001373358600232
The various spectrum data of the naphthalene of gained [1,2-b:5,6-b '] two thiophene are as follows.
1H-NMR(270MHz，CDCl 3)δ7.50(d，2H，J＝5.3Hz，ArH)，7.54(d，2H，J＝5.3Hz，ArH)，7.95(d，2H，J＝8.6Hz，ArH)，8.07(d，2H，J＝8.6Hz，ArH)；EIMS(70eV)m/z＝240(M +)；mp?150.4-150.8℃
Embodiment 8
Then, to 2, the synthetic of 7-hexichol naphthalene [1,2-b:5,6-b '] two thiophene sequentially describes.
1,5-two chloro-2, two (phenylacetylene) naphthalenes of 6-synthetic
Use synthetic 1 as previously mentioned, 5-two chloro-2, two (trifluoromethane sulphonyl) naphthalenes of 6-synthesize 1 by following mode, 5-two chloro-2, two (phenylacetylene) naphthalenes of 6-.
Under nitrogen atmosphere, with 1,5-two chloro-2, two (trifluoromethane sulphonyl) naphthalenes of 6-(493mg, 1.0mmol) and triethylamine (0.42mg 3.0mmol) is dissolved among the DMF (10ml).This solution is carried out the degassing in 30 minutes.
In this solution, add Pd (PPh as catalyzer 3) 2Cl 2(70mg, 0.1mmol, 10mol%) and CuI (38mg, 0.1mmol, 20mol%) and as the phenylacetylene of reagent (0.33ml, 3.0mmol).With its at room temperature stir reacted in 27 hours after, add pure water (1ml) and 1N hydrochloric acid (1ml), make to react to stop.
Use methylene dichloride (10ml) that this reaction soln is extracted.This extraction is carried out 3 times in an identical manner.After the extraction, use saturated aqueous common salt (10ml) that organic phase is cleaned.Should clean and carry out in an identical manner 3 times.
After using anhydrous magnesium sulfate that the moisture that contains in the organic phase is removed, under reduced pressure make solvent evaporation, obtain thick resultant.
By being that the silica gel column chromatography (Rf=0.2) that moves phase carries out separation and purification to this thick resultant with the normal hexane, further clean by normal hexane, obtain 1 of faint yellow solid, 5-two chloro-2, two (phenylacetylene) naphthalenes (180mg, yield 45%) of 6-.
The reaction formula of above-mentioned reaction is as follows.
Figure BPA00001373358600241
1 of gained, 5-two chloro-2, the various spectrum data of two (phenylacetylene) naphthalenes of 6-are as follows.
1H-NMR(270MHz，CDCl 3)δ7.39-7.42(m，6H，ArH)，7.63-7.67(m，4H，ArH)，7.74(d，2H，J＝8.6Hz，ArH)，8.25(d，2H，J＝8.6Hz，ArH)；EIMS(70eV)m/z＝396(M +)
2,7-hexichol naphthalene [1,2-b:5,6-b '] two thiophene synthetic
Under nitrogen atmosphere, make Na 2S9H 2O (608mg, 2.53mmol) outstanding turbid in NMP (15ml), stirred 15 minutes.
In this this suspension liquid, add 1,5-two chloro-2, (250mg 0.63mmol), stirred 12 hours down at 190 ℃ two (phenylacetylene) naphthalenes of 6-.After this reaction solution is cooled to room temperature, be injected in the saturated aqueous ammonium chloride (50ml).Filter and take out the solid of separating out.
By to this solid sublimation purifying, obtain 2,7-hexichol naphthalene [1,2-b:5,6-b '] two thiophene (147mg, 60%).
The reaction formula of above-mentioned reaction is as follows.
Figure BPA00001373358600242
2 of gained, the various spectrum data of 7-hexichol naphthalene [1,2-b:5,6-b '] two thiophene are as follows.
1H-NMR(270MHz，CDCl 3)δ7.34-7.40(m，2H，ArH)，7.45-7.57(m，4H，ArH)，7.71(s，2H，ArH)，7.79-7.82(m，4H，ArH)，7.91(d，2H，J＝8.6Hz，ArH)，8.05(d，2H，J＝8.6Hz，ArH)；EIMS(70eV)m/z＝392(M +)；mp＞300℃
Embodiment 9
Then, for 2, the synthetic of 7-dioctyl naphthalene [1,2-b:5,6-b '] two thiophene sequentially describes.
1,5-two chloro-2,6-two (decine-1-yl) naphthalene synthetic
Use synthetic 1 as previously mentioned, 5-two chloro-2, two (trifluoromethane sulphonyl) naphthalenes of 6-synthesize 1,5-two chloro-2,6-two (decine-1-yl) naphthalene in such a way.
Under nitrogen atmosphere, with 1,5-two chloro-2, two (trifluoromethane sulphonyl) naphthalenes of 6-(493mg, 1.0mmol) and triethylamine (0.42mg 3.0mmol) is dissolved among the DMF (10ml).This solution is carried out the degassing in 30 minutes.
In this solution, add Pd (PPh as catalyzer 3) 2Cl 2(70mg, 0.1mmol, 10mol%) and CuI (38mg, 0.1mmol, 20mol%) and as the 1-decine of reagent (0.54ml, 3.0mmol).With its at room temperature stir reacted in 27 hours after, add pure water (1ml) and 1N hydrochloric acid (1ml), make to react to stop.
Use methylene dichloride (10ml) that this reaction solution is extracted.This extraction is carried out 3 times in the same way.After the extraction, use saturated aqueous common salt (10ml) to clean organic phase.Should clean and carry out in the same way 3 times.
After using anhydrous magnesium sulfate that the moisture that contains in the organic phase is removed, make the solvent vapourisation under reduced pressure, obtain thick resultant.
By being that the silica gel column chromatography (RF=0.3) of migration phase carries out separation and purification to the thick resultant of gained with the normal hexane, obtain 1 of white solid, 5-two chloro-2,6-two (decine-1-yl) naphthalene (408mg, yield 87%).
The reaction formula of above-mentioned reaction is as follows.
Figure BPA00001373358600251
1 of gained, 5-two chloro-2, the various spectrum data of 6-two (decine-1-yl) naphthalene are as follows.
1H-NMR(270MHz，CDCl 3)δ0.89(t，6H，J＝7.0Hz，CH 3)，1.23-1.71(m，24H，CH 2)，2.53(t，4H，J＝7.0Hz，CH 2)，7.56(d，2H，J＝8.5Hz，ArH)，8.13(d，2H，J＝8.5Hz，ArH)；EIMS(70eV)m/z＝468(M +)
2,7-dioctyl naphthalene [1,2-b:5,6-b '] two thiophene synthetic
Under nitrogen atmosphere with Na 2S9H 2O (204mg, 0.85mmol) outstanding turbid in NMP (5ml), stirred 15 minutes.
In this suspension liquid, add 1,5-two chloro-2, (100mg 0.21mmol), stirred 13 hours down at 190 ℃ 6-two (decine-1-yl) naphthalene.After it is cooled to room temperature, be injected in the saturated aqueous ammonium chloride (30ml).Filter and take out the solid of separating out.
By being that the silica gel column chromatography (RF=0.5) that moves phase carries out separation and purification to this solid with the normal hexane, obtain 2 of white solid, 7-dioctyl naphthalene [1,2-b:5,6-b '] two thiophene (147mg, 60%).
The reaction formula of above-mentioned reaction is as follows.
Figure BPA00001373358600261
2 of gained, the various spectrum data of 7-dioctyl naphthalene [1,2-b:5,6-b '] two thiophene are as follows.
1H-NMR(270MHz，CDCl 3)δ0.88(t，6H，J＝6.8Hz，CH 3)，1.21-1.83(m，24H，CH 2)，2.97(t，4H，J＝7.4Hz，CH 2)，7.14(s，2H，ArH)，7.77(d，2H，J＝8.6Hz，ArH)，7.91(d，2H，J＝8.6Hz，ArH)；EIMS(70eV)m/z＝464(M +)；mp?92-93℃
Embodiment 10
Synthesizing of naphthalene [1,2-b:5,6-b '] two selenium phenol
Under nitrogen atmosphere, (72mg, 0.91mmol) outstanding turbid in ethanol (3ml), (34mg 0.91mmol), stirred 40 minutes further to add sodium borohydride under ice bath to make selenium.
In this suspension liquid, add NMP (10ml) and synthetic 1 as previously mentioned, 5-two chloro-2, (100mg 0.26mmol), stirred 12 hours down at 190 ℃ two (trimethylsilyl acetylene) naphthalenes of 6-.
After this reaction solution is cooled to room temperature, be injected in the saturated aqueous ammonium chloride (50ml).Filter and take out the solid of separating out.By being that the silica gel column chromatography (RF=0.2) that moves phase carries out separation and purification to this solid with the normal hexane, obtain naphthalene [1,2-b:5,6-b '] the two selenium phenol (70mg, yield 81%) of white solid.
The reaction formula of above-mentioned reaction is as follows.
The various spectrum data of the naphthalene of gained [1,2-b:5,6-b '] two selenium phenol are as follows.
1H-NMR(270MHz，CDCl 3)δ7.73(d，2H，J＝5.8Hz，ArH)，7.92(s，4H，ArH)，8.08(d，2H，J＝5.9Hz，ArH)； 13C-NMR(100MHz，CDCl 3)δ123.56，124.40，128.37，128.39，129.22，139.95，142.23；EIMS(70eV)m/z＝336(M +)
Embodiment 11
2,7-hexichol naphthalene [1,2-b:5,6-b '] two selenium phenol synthetic
Under nitrogen atmosphere, (141mg, 1.8mmol) outstanding turbid in ethanol (4ml), (68mg 1.8mmol), stirred 40 minutes to add sodium borohydride then under ice bath to make selenium.
In this suspension liquid, add NMP (20ml) and synthetic 1 as previously mentioned, 5-two chloro-2, (200mg, 0.5mmol), stirring is 12 hours under 190 degree for two (phenylacetylene) naphthalenes of 6-.After this reaction solution is cooled to room temperature, be injected in the saturated aqueous ammonium chloride (50ml).Filter and take out the solid of separating out.
This solid is made with extra care by thermograde heat sublimation method, obtained 2 of faint yellow solid, 7-hexichol naphthalene [1,2-b:5,6-b '] two selenium phenol (66mg, yield 27%).
The reaction formula of above-mentioned reaction is as follows.
Figure BPA00001373358600271
2 of gained, the spectrum data of 7-hexichol naphthalene [1,2-b:5,6-b '] two selenium phenol are as follows.Need to prove, because 2,7-hexichol naphthalene [1,2-b:5,6-b '] two selenium phenol are insolublies, can't carry out 1H-NMR measures.
EIMS(70eV)m/z＝488(M +)
Embodiment 12
Then, specify synthesis example by the represented compound of formula (4).
At first, synthetic for naphthalene [2,1-B:6,5-B '] two thiophene below sequentially describes.
2,6-two bromo-1,5-dihydroxy naphthlene synthetic
Under nitrogen atmosphere, with 1, (5.0g 31mmol) is dissolved in the acetic acid (150ml) with a spot of iodine the 5-dihydroxy naphthlene.This solution is heated to 80 ℃.Need to prove that the acetic acid here is as solvent.
(3.2ml, 62.4mmol), reaction is 12 hours under reflux temperature to splash into bromine in this solution.This reaction solution is cooled to room temperature, adds pure water (50ml).Filter and take out the solid of separating out.This solid under reduced pressure carries out drying after cleaning with pure water, obtains 2 of white solid, 6-two bromo-1,5-dihydroxy naphthlene (8.2g, yield 83%).
The reaction formula of above-mentioned reaction is as follows.
Figure BPA00001373358600272
2 of gained, 6-two bromo-1, the various spectrum data of 5-dihydroxy naphthlene are as follows.
1H-NMR(400MHz，CDCl 3)δ5.99(s，2H，OH)，7.39(d，2H，J＝9.4Hz，ArH)，7.70(d，2H，J＝9.4Hz，ArH)；EIMS(70eV)m/z＝318(M +)
2,6-two bromo-1, two (trifluoromethane sulphonyl) naphthalenes of 5-synthetic
Under nitrogen atmosphere, with 2,6-two bromo-1, the 5-dihydroxy naphthlene (3.0g, 9.4mmol) and pyridine (4.5ml 56mmol) is dissolved in the methylene dichloride (90ml).Here, pyridine is to be used to remove the not additive of thing, and methylene dichloride uses as solvent.
Under ice bath, in this solution, slowly add Trifluoromethanesulfonic anhydride (3.3ml, 21mmol).It after 4 hours 30 minutes, is added pure water (10ml) and 1N hydrochloric acid (10ml) in stirring at room, reaction is stopped.
Use methylene dichloride (20ml) that this reaction solution is extracted.Need to prove that this extraction is carried out 3 times in the same way.After the extraction, organic phase is cleaned with saturated aqueous common salt (20ml).Need to prove that this is cleaned and carries out in the same way 3 times.
After using anhydrous magnesium sulfate that the moisture that contains in the organic phase is removed, make the solvent vapourisation under reduced pressure, obtain thick resultant.
By being that the silica gel column chromatography (RF=0.95) that moves phase carries out separation and purification to this thick resultant with the methylene dichloride, obtain 2 of white solid, 6-two bromo-1, two (trifluoromethane sulphonyl) naphthalenes (3.2g, yield 58%) of 5-.
The reaction formula of above-mentioned reaction is as follows.
Figure BPA00001373358600281
2 of gained, 6-two bromo-1, the various spectrum data of two (trifluoromethane sulphonyl) naphthalenes of 5-are as follows.
1H-NMR(270MHz，CDCl 3)δ7.89(d，2H，J＝9.2Hz，ArH)，8.03(d，2H，J＝9.2Hz，ArH)；EIMS(70eV)m/z＝582(M +)
2,6-two bromo-1, two (trimethylsilyl acetylene) naphthalenes of 5-synthetic
Under nitrogen atmosphere, with 2,6-two bromo-1, (582mg 1.0mmol) is dissolved in DMF (7ml) and the Diisopropylamine (7ml) two (trifluoromethane sulphonyl) naphthalenes of 5-.This solution is carried out the degassing in 30 minutes.
In this solution, add Pd (PPh as catalyzer 3) 2Cl 2(70mg, 0.05mmol, 10mol%) and CuI (38mg, 0.1mmol, 20mol%) and as the trimethylsilyl acetylene of reagent (0.28ml, 2.0mmol).With its at room temperature stir stirred in 11 hours after, add pure water (1ml) and 1N hydrochloric acid (1ml), make to react to stop.
Use methylene dichloride (5ml) that this reaction solution is extracted.This extraction is carried out 3 times in the same way.After the extraction, use saturated aqueous common salt (5ml) that organic phase is cleaned.Should clean and carry out in the same way 3 times.
After using anhydrous magnesium sulfate that the moisture that contains in the organic phase is removed, make the solvent vapourisation under reduced pressure, obtain thick resultant.
By being that the silica gel column chromatography (RF=0.2) of migration phase carries out separation and purification to the thick resultant of gained with the normal hexane, obtain 2 of white solid, 6-two bromo-1, two (trimethylsilyl acetylene) naphthalenes (234mg, yield 49%) of 5-.
The reaction formula of above-mentioned reaction is as follows.
Figure BPA00001373358600291
2 of gained, 6-two bromo-1, the various spectrum data of two (trimethylsilyl acetylene) naphthalenes of 5-are as follows.
1H-NMR(270MHz，CDCl 3)δ0.29(s，18H，TMS)，7.71(d，2H，J＝8.8Hz，ArH)，8.14(d，2H，J＝8.8Hz，ArH)；EIMS(70eV)m/z＝478(M +)
Synthesizing of naphthalene [2,1-b:6,5-b '] two thiophene
Under nitrogen atmosphere, make Na 2S9H 2O (202mg, 0.84mmol) outstanding turbid in NMP (6ml), stirred 15 minutes.
In this suspension liquid, add 2,6-two bromo-1, (100mg 0.2mmol), stirred 14 hours down at 190 ℃ two (trimethylsilyl acetylene) naphthalenes of 5-.After it is cooled to room temperature, be injected in the saturated aqueous ammonium chloride (20ml).Filter and take out the solid of separating out.Obtain naphthalene [2,1-b:6,5-b '] two thiophene (62mg).
The reaction formula of above-mentioned reaction is as follows.
Figure BPA00001373358600292
The various spectrum data of the naphthalene of gained [2,1-B:6,5-B '] two thiophene are as follows.
1H-NMR(270MHz，CDCl 3)δ7.43(d，2H，J＝5.4Hz，ArH)，8.05(d，2H，J＝5.5Hz?ArH)，8.05(d，2H，J＝8.9Hz，ArH)，8.30(d，2H，J＝8.9Hz，ArH)；EIMS(70eV)m/z＝240(M +)
Embodiment 13
Then, for 2, synthesizing of 7-hexichol naphthalene [2,1-B:6,5-B '] two thiophene sequentially describes.
2,6-two bromo-1, two (phenylacetylene) naphthalenes of 5-synthetic
Use synthetic 2 as previously mentioned, 6-two bromo-1, two (trifluoromethane sulphonyl) naphthalenes of 5-, Synthetic 2 in the following manner, 6-two bromo-1, two (phenylacetylene) naphthalenes of 5-.
Under nitrogen atmosphere with 2,6-two bromo-1, (582mg 1.0mmol) is dissolved in DMF (7ml) and the Diisopropylamine (7ml) two (trifluoromethane sulphonyl) naphthalenes of 5-.This solution is carried out the degassing in 30 minutes.
In this solution, add Pd (PPh as catalyzer 3) 2Cl 2(70mg, 0.05mmol, 10mol%) and CuI (38mg, 0.1mmol, 20mol%) and as the phenylacetylene of reagent (0.22ml, 2.0mmol).With its at room temperature stir reacted in 11 hours after, add pure water (1ml) and 1N hydrochloric acid (1ml), make to react to stop.
Use methylene dichloride (5ml) that this reaction solution is extracted.This extraction is carried out 3 times in the same way.After the extraction, organic phase is cleaned with saturated aqueous common salt (5ml).Should clean and carry out in the same way 3 times.
After using anhydrous magnesium sulfate that the moisture that contains in the organic phase is removed, make the solvent vapourisation under reduced pressure, obtain thick resultant.
By being that the silica gel column chromatography (Rf=0.1) that moves phase carries out separation and purification to this thick resultant with the normal hexane, obtain 2 of white solid, 6-two bromo-1, two (phenylacetylene) naphthalenes (437mg, yield 90%) of 5-.
The reaction formula of above-mentioned reaction is as follows.
Figure BPA00001373358600301
2 of gained, 6-two bromo-1, the various spectrum data of two (phenylacetylene) naphthalenes of 5-are as follows.
1H-NMR(270MHz，CDCl 3)δ7.42-7.44(m，6H，ArH)，7.69-7.72(m，4H，ArH)，7.79(d，2H，J＝8.9Hz，ArH)，8.27(d，2H，J＝8.9Hz，ArH)；EIMS(70eV)m/z＝486(M +)
2,7-hexichol naphthalene [2,1-B:6,5-B '] two thiophene synthetic
Under nitrogen atmosphere, make Na 2S9H 2O (404mg, 1.68mmol) outstanding turbid in NMP (12ml), stirred 15 minutes.
In this this suspension liquid, add 2,6-two bromo-1, (200mg 0.4mmol), stirred 14 hours down at 190 ℃ two (phenylacetylene) naphthalenes of 5-.After it is cooled to room temperature, be injected in the saturated aqueous ammonium chloride (20ml).Filtration is also taken out the solid of separating out, and obtains 2 thus, 7-hexichol naphthalene [2,1-B:6,5-B '] two thiophene (192mg).
The reaction formula of above-mentioned reaction is as follows.
Figure BPA00001373358600302
2 of gained, the various spectrum data of 7-hexichol naphthalene [2,1-B:6,5-B '] two thiophene are as follows.
1H-NMR(400MHz，CDCl 3)δ7.39-7.40(m，2H，ArH)，7.47-7.51(m，4H，ArH)，7.82-7.84(m，4H，ArH)，8.01(d，2H，J＝8.6Hz，ArH)，7.71(s，2H，ArH)，8.05(d，2H，J＝8.6Hz，ArH)；EIMS(70eV)m/z＝392(M +)
Embodiment 14
Then, about 2, synthesizing of 7-dioctyl naphthalene [2,1-b:6,5-b '] two thiophene sequentially describes.
2,6-two bromo-1,5-two (decine-1-yl) naphthalene synthetic
Use synthetic 2 as previously mentioned, 6-two bromo-1, two (trifluoromethane sulphonyl) naphthalenes of 5-, Synthetic 2 in the following manner, 6-two bromo-1,5-two (decine-1-yl) naphthalene.
Under nitrogen atmosphere, with 2,6-two bromo-1, (582mg 1.0mmol) is dissolved in DMF (7ml) and the Diisopropylamine (7ml) two (trifluoromethane sulphonyl) naphthalenes of 5-.This solution is carried out the degassing in 30 minutes.
In this solution, add Pd (PPh as catalyzer 3) 2Cl 2(70mg, 0.05mmol, 10mol%) and CuI (38mg, 0.1mmol, 20mol%) and as the 1-decine of reagent (0.36ml, 2.0mmol).With its at room temperature stir reacted in 11 hours after, add pure water (1ml) and 1N hydrochloric acid (1ml), make to react to stop.
Use methylene dichloride (5ml) that this reaction solution is extracted.This extraction is carried out 3 times in the same way.After the extraction, use saturated aqueous common salt (5ml) that organic phase is cleaned.Should clean and carry out in the same way 3 times.
After using anhydrous magnesium sulfate that the moisture that contains in the organic phase is removed, make the solvent vapourisation under reduced pressure, obtain thick resultant.
By being that the silica gel column chromatography (RF=0.2) that moves phase carries out separation and purification to this thick resultant with the normal hexane, obtain 2 of white solid, 6-two bromo-1,5-two (decine-1-yl) naphthalene (340mg, yield 61%).
The reaction formula of above-mentioned reaction is as follows.
2 of gained, 6-two bromo-1, the various spectrum data of 5-two (decine-1-yl) naphthalene are as follows.
1H-NMR(270MHz，CDCl 3)δ0.89(t，6H，J＝7.0Hz，CH 3)，1.26-1.70(m，24H，CH 2)，2.62(t，4H，J＝7.3Hz，CH 2)，7.68(d，2H，J＝9.4Hz，ArH)，8.10(d，2H，J＝9.4Hz，ArH)；EIMS(70eV)m/z＝558(M +)
2,7-dioctyl naphthalene [2,1-b:6,5-b '] two thiophene synthetic
Under nitrogen atmosphere, make Na 2S9H 2O (404mg, 1.68mmol) outstanding turbid in NMP (12ml), stirred 15 minutes.
In this suspension liquid, add 2,6-two bromo-1, (200mg 0.4mmol), stirred 14 hours down at 190 ℃ 5-two (decine-1-yl) naphthalene.After it is cooled to room temperature, be injected in the saturated aqueous ammonium chloride (20ml).Filtration is also taken out the solid of separating out, and obtains 2 thus, 7-dioctyl naphthalene [2,1-b:6,5-b '] two thiophene (200mg, yield 100%).
The reaction formula of above-mentioned reaction is as follows.
Figure BPA00001373358600321
2 of gained, the various spectrum data of 7-dioctyl naphthalene [2,1-B:6,5-B '] two thiophene are as follows.
1H-NMR(400MHz，CDCl 3)δ0.88(t，6H，J＝7.0Hz，CH 3)，1.26-1.70(m，24H，CH 2)，3.02(t，4H，J＝7.3Hz，CH 2)，7.68(s，2H，ArH)，7.89(d，2H，J＝8.8Hz，ArH)，8.12(d，2H，J＝8.8Hz，ArH)；EIMS(70eV)m/z＝464(M +)
Embodiment 15
Then, based on embodiment the synthesis example by the represented compound of formula (5) is specifically described.
2,7-dibromine naphthalene [2,3-b:6,7-b '] two thiophene synthetic
Under nitrogen atmosphere, make synthetic naphthalene in embodiment 1 [2,3-b:6,7-b '] two thiophene (50mg, 0.21mmol) outstanding turbid in THF (10ml).This suspension liquid is cooled to-78 ℃, and adding n-BuLi (0.4ml, 0.63mmol, 1.59M).Its stirring after 30 minutes, is splashed into 1,2-two bromo-sym.-tetrachloroethane (150mg, THF 0.46mmol) (3ml) solution.
Then, this reaction solution is warming up to room temperature, stirs after 16 hours, add pure water (1ml) and 1N hydrochloric acid (1ml) reaction is stopped.Filtration is also taken out the solid of separating out, and obtains 2,7-dibromine naphthalene [2,3-b:6,7-b '] two thiophene (15mg, yield 18%).
The reaction formula of above-mentioned reaction is as follows.
Figure BPA00001373358600322
2 of gained, the various spectrum data of 7-dibromine naphthalene [2,3-b:6,7-b '] two thiophene are as follows.
1H-NMR(400MHz，CDCl 3)δ7.43(s，2H，ArH)，8.22(s，2H，ArH)，8.31(s，2H，ArH)；
EIMS(70eV)m/z＝398(M +)
Embodiment 16
Then, synthetic for by the represented compound of formula (7) is specifically described based on embodiment.
2,7-dibromine naphthalene [1,2-b:5,6-b '] two thiophene synthetic
Under nitrogen atmosphere, (50mg 0.21mmol) is dissolved among the THF (5ml) with synthetic naphthalene among the embodiment 7 [1,2-b:5,6-b '] two thiophene.This solution is cooled to-78 ℃, and adding n-BuLi (0.4ml, 0.63mmol, 1.59M).Its stirring after 30 minutes, is splashed into 1,2-two bromo-1,1,2,2 ,-tetrachloroethane (651mg, THF 2mmol) (3ml) solution.
This reaction solution is warming up to room temperature, stirs after 16 hours, add pure water (1ml) and 1N hydrochloric acid (1ml) reaction is stopped.Use methylene dichloride (5ml) that this reaction solution is extracted.This extraction is carried out 3 times in the same way.After the extraction, use saturated aqueous common salt (5ml) that organic phase is cleaned.Should clean and carry out in the same way 3 times.
After using anhydrous magnesium sulfate that the moisture that contains in the organic phase is removed, under reduced pressure make solvent evaporation, obtain thick resultant.By being that the silica gel column chromatography (RF=0.95) of migration phase carries out separation and purification to the thick resultant of gained with the methylene dichloride, obtain 2 of white solid, 7-dibromine naphthalene [1,2-b:5,6-b '] two thiophene (68mg, yield 81%).
The reaction formula of above-mentioned reaction is as follows.
Figure BPA00001373358600331
2 of gained, the various spectrum data of 7-dibromine naphthalene [1,2-b:5,6-b '] two thiophene are as follows.
1H-NMR(270MHz，CDCl 3)δ7.48(s，2H，ArH)，7.80(d，2H，J＝8.5Hz，ArH)，7.87(d，2H，J＝8.5Hz，ArH)；EIMS(70eV)m/z＝398(M +)
Embodiment 17
2,7-diiodonaphthalene [1,2-b:5,6-b '] two thiophene synthetic
Under nitrogen atmosphere, (50mg 0.21mmol) is dissolved among the THF (5ml) with synthetic naphthalene among the embodiment 7 [1,2-b:5,6-b '] two thiophene.This solution is cooled to-78 ℃, and adding n-BuLi (0.4ml, 0.63mmol, 1.59M).Its stirring after 30 minutes, is splashed into iodine (117mg, THF 0.46mmol) (3ml) solution.
This reaction solution is warming up to room temperature, stirs after 10 hours, add pure water (1ml) and 1N hydrochloric acid (1ml) reaction is stopped.Filter and take out, obtain 2 of white solid thus, 7-diiodonaphthalene [1,2-b:5,6-b '] two thiophene (82mg, yield 80%) the solid of separating out.
The reaction formula of above-mentioned reaction is as follows.
Figure BPA00001373358600332
2 of gained, the various spectrum data of 7-diiodonaphthalene [1,2-b:5,6-b '] two thiophene are as follows.
1H-NMR(270MHz，CDCl 3)δ7.68(s，2H，ArH)，7.82(d，2H，J＝8.8Hz，ArH)，7.86(d，2H，J＝8.8Hz，ArH)；EIMS(70eV)m/z＝492(M +)
Embodiment 18
The FET characteristic
Use synthetic 2 among the embodiment 2,7-hexichol naphthalene [2,3-b:6,7-b '] synthetic 2 in two thiophene (hereinafter referred to as compd A), embodiment 3,7-dioctyl naphthalene [2,3-b:6,7-b '] synthetic 2 in two thiophene (hereinafter referred to as compd B), embodiment 8,7-hexichol naphthalene [1,2-b:5,6-b '] synthetic 2 in two thiophene (hereinafter referred to as Compound C), embodiment 11,7-hexichol naphthalene [1,2-b:5,6-b '] two selenium phenol (hereinafter referred to as Compound D), prepare the FET element respectively, check its FET characteristic.
As the FET element of compd A is used in the preparation of getting off.At first, cut the SiO of area 1cm * 1cm size 2Substrate.To this SiO 2Handle with hydrofluoric acid at the back side of substrate, removes the silicon of oxidation in air.Then, at SiO 2Vacuum evaporation Au forms gate electrode on the substrate.At this SiO 2Form the organic film of compd A on the substrate surface by vacuum vapour deposition.Need to prove employed SiO 2Substrate has been implemented surface treatment by the octyl group trichlorosilane.
On the organic film of the compd A that forms, use shadow mask (shadow mask) and vacuum evaporation Au, form source electrode and drain electrode.
The schematic configuration of the FET element of preparation is shown in Fig. 1 (Fig. 1 (A) is that sectional view, Fig. 1 (B) of FET element is the orthographic plan of FET element).The FET element of preparation is the top contact type.Its channel length is 50 μ m, and channel width is 1.5mm.
With similarly above-mentioned, the FET element of Compound C and the FET element of use Compound D are used in preparation respectively.
In addition, the FET element that uses compd B for preparing as follows.At first, cut the SiO of area 1cm * 1cm size 2Substrate.To this SiO 2The back side of substrate is handled by hydrofluoric acid, to remove the silicon of oxidation in air.Then, at SiO 2Vacuum evaporation Au on the substrate forms gate electrode.At this SiO 2Pass through spin-coating method (organic film preparation condition: 3000rpm, 30sec) organic film of formation compd B on the substrate surface.Need to prove, at this moment use its chloroformic solution (concentration 0.4wt%) as compd B.
On the organic film of the compd B that forms, use shadow mask and vacuum evaporation Au, form source electrode and drain electrode.Need to prove that the structure of this FET element etc. are identical with above-mentioned other FET element.
The performance of FET element depends on and gate electrode is being applied under the state of voltage the magnitude of current that flows through when applying voltage between source electrode and drain electrode.By measuring this current value, can determine electric field mobility as the FET element characteristic.Electric field mobility can be by expressing as the SiO that is applied to as isolator 2On the formula (a) of electrical specification of the current carrier kind result, that produce in the organic semiconductor layer of gate voltage obtain.
Id＝WμC O(Vg-Vt) 2/2L …(a)
In the formula (a), Id is saturated source-leakage current value, and W is a channel width, C OBe gate capacitance, Vg is a gate voltage, and Vt is that threshold voltage, L are channel length.μ is the electric field mobility (cm according to the definite FET element of mensuration 2/ Vs).C OBy employed SiO 2The specific inductivity decision of insulating film.W and L are by the component structure decision of FET element.Id and Vg can the current value of measuring the FET element the time determine.Vt can be obtained by Id, Vg.With each value substitution formula (a), can calculate the electric field mobility under the gate voltage separately.Need to prove that threshold voltage is to be Y-axis, Vg when being the X-axis mapping by the square root with-Id, Vg value conduct " Vt " value when curve rises is obtained.
For FET element separately, in order to study its p type FET characteristic, apply negative gate voltage, in atmosphere, drive, and estimate.
Fig. 2 is the figure that shows the FET characteristic of the FET element that uses the compd A preparation.Fig. 3 is the figure that shows the FET characteristic of the FET element that uses the compd B preparation.Fig. 4 is the figure that shows the FET characteristic of the FET element that uses the Compound C preparation.In addition, Fig. 5 is the figure that shows the FET characteristic of the FET element that uses the Compound D preparation.
Here, Fig. 2 (A), Fig. 3 (A), Fig. 4 (A) and Fig. 5 (A) are the Vg-Id curves of FET element separately.In addition, Fig. 2 (B), Fig. 3 (B), Fig. 4 (B) and Fig. 5 (B) are the Vd-Id curves of FET element separately.
Gate voltage (Vg) during the value of the electric current of the voltage (Vd) between the stationary source-leakage in the Vg-Id curve representation output characteristic and the relation between the electric current (Id) so that electric current (Id) reaches capacity.That is the conversion characteristic (transport property) of this FET element of Vg-Id curve representation.In this Vg-Id curve, the rise from the off state to the on state is rapid more, represents that then switching characteristic is good, and it is good promptly to be called transistor characteristic.In addition, if the off electric current is low more, and the on electric current is high more, and then on/off is bigger than more, so just represents good transistor.
Voltage (Vd) between the source-leakage when on the other hand, the Vd-Id curve representation sequentially changes gate voltage (Vg) and the relation between the electric current (Id).That is the output characteristic of this FET element of Vd-Id curve representation.For in this FET element under any gate voltage (Vg), as long as demonstrate voltage (Vd) between source-leakage at higher electric current (Id) reach capacity (saturation currnet) when regional, and electric current (Id) straight line rises during lower regional of the voltage between source-leakage (Vd), we can say that then this FET element has good output characteristics, is high performance.
Referring to Fig. 2 (A), Fig. 3 (A), Fig. 4 (A) and Fig. 5 (A), by applying gate voltage (Vg), the electric current of any (Id) all sharply rises.This switching characteristic that shows FET element of the present invention is good.In addition, referring to Fig. 2 (B), Fig. 3 (B), Fig. 4 (B) and Fig. 5 (B), when regional, the Vd-Id curve all is to rise point-blank to the voltage between source-leakage (Vd) lower, and the voltage between source-leakage (Vd) higher when regional leakage current keep certain, observe saturation currnet.This shows that FET element of the present invention has good output characteristics, is high performance FET element.
Then, obtain the electric field mobility of each FET element based on aforesaid method.In addition, in Vg-Id curve separately, little as 0 with the value of Vg～-be the off state during 10V, be the on state with Vg during for-60V, obtain the ratio of value of the Id separately of off state and on state, as the on/off ratio.The result is as described below.Use in the FET element of compd A, electric field mobility is 0.7cm 2/ Vs, on/off ratio is 10 6Use in the FET element of Compound C, electric field mobility is 0.2cm 2/ Vs, on/off ratio is 10 7In addition, use in the FET element of Compound D, electric field mobility is 0.2cm 2/ Vs, on/off ratio is 10 7Like this, use the FET element of compd A, Compound C, Compound D all to demonstrate good measurement result.
In addition, use compd B, be 10 by the electric field mobility of the FET element of coating method preparation -3Cm 2About/Vs, in addition, the on/off ratio is 10 5, be in a ratio of relatively poor slightly result with the FET element that uses compd A, Compound C and Compound D.But,,, also can utilize coating method as can be known as the preparation method of FET element of the present invention because this FET element also possesses the FET characteristic.
Like this, use the FET element of synthetic compd A, compd B, Compound C and Compound D in the present embodiment, can use as the p transistor npn npn.
The application's basis is Japanese patent application 2008-298830 number of filing an application on November 21st, 2008 and Japanese patent application 2009-080527 number of filing an application on March 27th, 2009.In this specification sheets by with reference to and whole specification sheets, claims and the accompanying drawing of having incorporated Japanese patent application 2008-298830 number and 2009-080527 number into.
Utilizability on the industry
Compound of the present invention is because the interaction of π track has conjugated system at intramolecularly, further demonstrates intermolecular than strong interaction that the sulphur atom that contains in thiphene ring by each molecule or the selenium phenol ring or selenium atom produce.Therefore, compound of the present invention can carry out mobility of charge carrier effectively.Such compound can be used as organic semiconductor material because of having good electric field mobility, further can constitute the organic semiconductor device that uses this organic semiconductor material.

Claims (16)

1. compound, it is served as reasons with following formula (1), formula (2), formula (3) or the represented compound of formula (4),
Figure FPA00001373358500011
In the above-mentioned formula, Z represents sulphur atom or selenium atom, and R represents hydrogen atom, alkyl or phenyl.
2. compound, it is served as reasons with following formula (5), formula (6), formula (7) or the represented compound of formula (8),
Figure FPA00001373358500012
In the above-mentioned formula, Z represents sulphur atom or selenium atom, and X represents halogen atom.
3. the preparation method of a compound, described compound is served as reasons with following formula (1), formula (2), formula (3) or the represented compound of formula (4), may further comprise the steps:
Make dihalo-dihydroxy naphthlene and Trifluoromethanesulfonic anhydride react the step of acquisition dihalo--two (trifluoromethane sulphonyl) naphthalene;
Make described dihalo--two (trifluoromethane sulphonyl) naphthalenes and terminal alkynyl compounds react the step of acquisition dihalo--diacetylene naphthalene derivatives; And
The step that above-mentioned dihalo--diacetylene naphthalene derivatives and sulphide salt or selenide salt are reacted,
Figure FPA00001373358500021
In the above-mentioned formula, Z represents sulphur atom or selenium atom, and R represents hydrogen atom, alkyl or phenyl.
4. the preparation method of compound as claimed in claim 3 is characterized in that, and is further comprising the steps of:
Make dihydroxy naphthlene and halogenating agent react the step that obtains described dihalo-dihydroxy naphthlene.
5. the preparation method of compound as claimed in claim 4 is characterized in that,
Described dihydroxy naphthlene is 2, the 6-dihydroxy naphthlene,
The compound that is obtained is by described formula (1) or the represented compound of described formula (3).
6. the preparation method of compound as claimed in claim 4 is characterized in that,
Described dihydroxy naphthlene is a 2,7 dihydroxy naphthalene,
The compound that is obtained is by the represented compound of described formula (2).
7. the preparation method of compound as claimed in claim 4 is characterized in that,
Described dihydroxy naphthlene is 1, the 5-dihydroxy naphthlene,
The compound that is obtained is by the represented compound of described formula (4).
8. the preparation method of compound as claimed in claim 4 is characterized in that,
Described halogenating agent is bromizating agent or chlorizating agent.
9. the preparation method of compound as claimed in claim 8 is characterized in that,
Described halogenating agent is a bromizating agent,
The step that also comprises the catalyzer that adds the bromination that promotes described dihydroxy naphthlene,
Adding the step of described bromizating agent carries out more than 2 times.
10. the preparation method of compound as claimed in claim 3 is characterized in that,
Described terminal alkynyl compounds is any in trimethylsilyl acetylene, phenylacetylene, the 1-decine.
11. the preparation method of compound as claimed in claim 3 is characterized in that,
The reaction of described dihalo--two (trifluoromethane sulphonyl) naphthalene and described terminal alkynyl compounds is to carry out in the polar solvent that can dissolve described dihalo--two (trifluoromethane sulphonyl) naphthalene.
12. the preparation method of compound as claimed in claim 11 is characterized in that,
Described polar solvent is non-protic polar solvent.
13. the preparation method of compound as claimed in claim 12 is characterized in that,
Described non-proton property polar solvent is a dimethyl formamide.
14. one kind by the preparation method with the represented compound of following formula (5), formula (6), formula (7) or formula (8),
Above-mentioned various in, Z represents sulphur atom or selenium atom, X represents halogen atom,
It is characterized in that, may further comprise the steps:
By the step of adding halogenating agent in the represented compound of following formula (1), formula (2), formula (3) or formula (4),
Figure FPA00001373358500032
Above-mentioned various in, Z represents sulphur atom or selenium atom, X represents halogen atom.
15. an organic semiconductor material is characterized in that, contains more than one by with following formula (1), formula (2), formula (3) or the represented compound of formula (4),
Figure FPA00001373358500041
In the above-mentioned formula, Z represents sulphur atom or selenium atom, and R represents hydrogen atom, alkyl or phenyl.
16. an organic semiconductor device is characterized in that, contains the described organic semiconductor material of claim 15.
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